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1

Spectroscopy and reactions of molecules important in chemical evolution  

NASA Technical Reports Server (NTRS)

The research includes: (1) hot hydrogen atom reactions in terms of the nature of products produced, mechanism of the reactions and the implication and application of such reactions for molecules existing in interstellar clouds, in planetary atmospheres, and in chemical evolution; (2) photochemical reactions that can lead to molecules important in chemical evolution, interstellar clouds and as constituents in planetary atmospheres; and (3) spectroscopic and theoretical properties of biomolecules and their precursors and where possible, use these to understand their photochemical behavior.

Becker, R. S.

1974-01-01

2

Chemical Reactions  

NSDL National Science Digital Library

We don't often stop to think about it, but underlying many of our everyday activities are chemical reactions. From the cooking of an egg to the growth of a child, chemical reactions make things happen. Although many of the reactions that support our lives

National Science Teachers Association (NSTA)

2009-05-01

3

Studies of Elementary Reactions of Chemical Importance in the Atmospheres of Planets  

NASA Technical Reports Server (NTRS)

The paper discusses the following: 1. F + Cl2 Kinetics. Absolute rate constant for the reaction F(P-2) with Cl2 has been measured using the discharge flow kinetics technique coupled to mass spectrometric detection at T = 180 - 360 K and 1 Torr He nominal pressure. 2. Vapor pressure system. The main effort on the vapor pressure system involved the design and construction of an insulated enclosure ("Bakeout Box") to improve the uniformity of heating during the bakeout process. 3. Sunphotometer System. This period saw the completion of the two-channel sunphotometer, its calibration, and two field deployments. 4. Vibrational-to-translation (V-T) transfer rates for light hydrocarbons at low temperatures are important parameters in thermal-structure models of the upper atmospheres of the outer planets and their satellites. However, the required data are either simply not available or do not extend to the low temperatures found in those systems. Because methane is such an important constituent in outer planet atmospheres, we have initiated a program to measure the temperature dependence of (V-T) rates for its relaxation by appropriate collision partners. 5. The central focus of this research has been the vapor phase nucleation and growth of metals/refractory species into small particles and the aggregation of these primary particles into larger structures. These topics are part of the broader goal of understanding the conditions under which interstellar dust grains condense from stellar outflows and how these small dust grains coagulate into larger bodies such as planetesimals or planets.

Nesbitt, Fred L.

2003-01-01

4

Microfluidic chemical reaction circuits  

DOEpatents

New microfluidic devices, useful for carrying out chemical reactions, are provided. The devices are adapted for on-chip solvent exchange, chemical processes requiring multiple chemical reactions, and rapid concentration of reagents.

Lee, Chung-cheng (Irvine, CA); Sui, Guodong (Los Angeles, CA); Elizarov, Arkadij (Valley Village, CA); Kolb, Hartmuth C. (Playa del Rey, CA); Huang, Jiang (San Jose, CA); Heath, James R. (South Pasadena, CA); Phelps, Michael E. (Los Angeles, CA); Quake, Stephen R. (Stanford, CA); Tseng, Hsian-rong (Los Angeles, CA); Wyatt, Paul (Tipperary, IE); Daridon, Antoine (Mont-Sur-Rolle, CH)

2012-06-26

5

Studies of Elementary Reactions of Chemical Importance in the Atmospheres of Planets  

NASA Technical Reports Server (NTRS)

The methyl self-reaction was studied at T = 298 K and 202 K and at three different pressures, P = 0.5, 1.0, and 2.1 Torr. The experimental measurements were performed in our discharge flow-mass spectrometer (DF-MS) apparatus. The methyl radicals were generated by the reaction of F with methane. Passing a mixture of molecular fluorine, F2, in helium through a microwave cavity generated the atomic fluorine reagent. The atomic F enters the flow tube through a rear port on the flow tube. The methane reagent enters the flow tube through a movable injector located coaxial in the flow tube. The decay of methyl radical signal was monitored at a mass/charge ratio (m/z) of 15 as a function of the injector distance. To minimize secondary chemistry from the reaction CH3 + F to CH2 + HF the initial [CH4](sub 0)/[F](sub 0) was above 37.0 and typically 100. This ensures a 1:1 relationship between initial [F] and [CH3]. A titration of F with excess Cl2 yields the initial [F](sub 0). Our experimental methodology to accurately measure the mass spectrometer scaling factor, i.e., the relationship between initial signal and [CH3](sub 0) has been improved. Now we measure the CH3 signal decay under exponential decay conditions at low initial [F](sub 0), 3x10(exp 11) molecule/cc, in the presence of Cl2. This minimizes the second-order decay contributed by the CH3 self-reaction and a simple extrapolation of the 1n(signal) vs time plot to t = 0 gives the initial signal. This provides the desired relationship between initial signal at 15 amu and [CH3](sub 0). The resulting calibration is then applied to the observed decay of the CH3 signal at high concentrations of CH3 assuming linearity of this scaling factor.

Nesbitt, Fred L.

2001-01-01

6

Chemical Reactions (Netorials)  

NSDL National Science Digital Library

Chemical Reactions: this is a resource in the collection "Netorials". The Netorials cover selected topics in first-year chemistry including: Chemical Reactions, Stoichiometry, Thermodynamics, Intermolecular Forces, Acids & Bases, Biomolecules, and Electrochemistry.

7

Chemical Reactions at Surfaces  

SciTech Connect

Chemical reactions at surfaces underlie some of the most important processes of today, including catalysis, energy conversion, microelectronics, human health and the environment. Understanding surface chemical reactions at a fundamental level is at the core of the field of surface science. The Gordon Research Conference on Chemical Reactions at Surfaces is one of the premiere meetings in the field. The program this year will cover a broad range of topics, including heterogeneous catalysis and surface chemistry, surfaces in environmental chemistry and energy conversion, reactions at the liquid-solid and liquid-gas interface, electronic materials growth and surface modification, biological interfaces, and electrons and photons at surfaces. An exciting program is planned, with contributions from outstanding speakers and discussion leaders from the international scientific community. The conference provides a dynamic environment with ample time for discussion and interaction. Attendees are encouraged to present posters; the poster sessions are historically well attended and stimulate additional discussions. The conference provides an excellent opportunity for junior researchers (e.g. graduate students or postdocs) to present their work and interact with established leaders in the field.

Michael Henderson and Nancy Ryan Gray

2010-04-14

8

Chemical Reactions and Stoichiometry  

NSDL National Science Digital Library

In this activity, students explore reactions in which chemical bonds are formed and broken. Students experiment with changing the temperature and the concentration of the atoms in order to see how these affect reaction rates. They also learn how to communicate what happens during a chemical reaction by writing the ratios of reactants and products, known as stoichiometry.

The Concord Consortium

2011-12-11

9

Oscillating Chemical Reactions  

ERIC Educational Resources Information Center

Describes several oscillating chemical reactions which can be used in undergraduate chemistry laboratories. In one such reaction, ferroin oscillates from red (reducing solution) to blue (oxidizing solution) for about an hour at a frequency which can readily be shown to depend on such factors as the temperature, type of solvent, and concentration…

Hawkins, M. D.; And Others

1975-01-01

10

Chemical Reactions in DSMC  

SciTech Connect

DSMC simulations of chemically reacting gas flows have generally employed procedures that convert the macroscopic chemical rate equations to reaction cross-sections at the microscopic level. They therefore depend on the availability of experimental data that has been fitted to equations of the Arrhenius form. This paper presents a physical model for dissociation and recombination reactions and a phenomenological model for exchange and chain reactions. These are based on the vibrational states of the colliding molecules and do not require any experimentally-based data. The simplicity of the models allows the corresponding rate equations to be written down and, while these are not required for the implementation of the models, they facilitate their validation. The model is applied to a typical hypersonic atmospheric entry problem and the results are compared with the corresponding results from the traditional method. It is also used to investigate both spontaneous and forced ignition as well as the structure of a deflagration wave in an oxygen-hydrogen mixture.

Bird, G. A. [GAB Consulting Pty Ltd, 144/110 Sussex Street, Sydney NSW 2000 (Australia)

2011-05-20

11

Chemical Reactions: Investigating Exothermic and Endothermic Reactions  

NSDL National Science Digital Library

This activity is an inquiry-based investigation where students discover the indicators of chemical reactions (endothermic and exothermic) by collecting data and using that data to develop a testable question for further experimentation.

12

More on Chemical Reaction Balancing.  

ERIC Educational Resources Information Center

A previous article stated that only the matrix method was powerful enough to balance a particular chemical equation. Shows how this equation can be balanced without using the matrix method. The approach taken involves writing partial mathematical reactions and redox half-reactions, and combining them to yield the final balanced reaction. (JN)

Swinehart, D. F.

1985-01-01

13

Chemical burn or reaction  

MedlinePLUS

... different products that contain toxic chemicals such as ammonia and bleach. The mixture can give off hazardous ... safely immediately after use. Use paints, petroleum products, ammonia, bleach, and other products that give off fumes ...

14

LEGO® Chemical Reactions  

NSDL National Science Digital Library

This activity uses LEGO® bricks to represent atoms bonding into molecules and crystals. The lesson plan is for a 2.5 hour workshop (or four 45-minute classes). There is a "wet lab" chemistry experiment (mixing baking soda and calcium chloride with phenol red indicator), followed by a "LEGO lab" modeling phase that includes writing formulas using chemical notation. This lesson is also offered as a 2.5 hour field trip lesson at the MIT Edgerton Center.

2014-09-29

15

Experimental Demonstrations in Teaching Chemical Reactions.  

ERIC Educational Resources Information Center

Presents demonstrations of chemical reactions by employing different features of various compounds that can be altered after a chemical change occurs. Experimental activities include para- and dia-magnetism in chemical reactions, aluminum reaction with base, reaction of acid with carbonates, use of electrochemical cells for demonstrating chemical

Hugerat, Muhamad; Basheer, Sobhi

2001-01-01

16

Homeostasis in Chemical Reaction Pathways  

E-print Network

We consider stochastic models of chemical reaction networks with time dependent input rates and several types of molecules. We prove that, in despite of strong time dependence of input rates, there is a kind of homeostasis phenomenon: far away from input nodes the mean numbers of molecules of each type become approximately constant (do not depend on time).

Malyshev, V A; Zamyatin, A A

2011-01-01

17

Homeostasis in Chemical Reaction Pathways  

E-print Network

We consider stochastic models of chemical reaction networks with time dependent input rates and several types of molecules. We prove that, in despite of strong time dependence of input rates, there is a kind of homeostasis phenomenon: far away from input nodes the mean numbers of molecules of each type become approximately constant (do not depend on time).

V. A. Malyshev; A. D. Manita; A. A. Zamyatin

2011-12-25

18

Spin uncoupling in chemical reactions  

Microsoft Academic Search

Spin pairing is the main attribute of the covalent chemical bond. Exchange repulsion between closed shell molecules being responsible for activation barriers in bimolecular reactions can be explained by a high weight of the intermolecular triplet spin pairing. Intermolecular exchange interaction switches to a strong attraction when the molecules are in excited triplet states. This is the reason for that

Boris F. Minaev; Hans Ågren

2001-01-01

19

Mineralogical and chemical assessment of concrete damaged by the oxidation of sulfide-bearing aggregates: Importance of thaumasite formation on reaction mechanisms  

SciTech Connect

Damages in concrete containing sulfide-bearing aggregates were recently observed in the Trois-Rivieres area (Quebec, Canada), characterized by rapid deterioration within 3 to 5 years after construction. A petrographic examination of concrete core samples was carried out using a combination of tools including: stereomicroscopic evaluation, polarized light microscopy, scanning electron microscopy, X-ray diffraction and electron microprobe analysis. The aggregate used to produce concrete was an intrusive igneous rock with different metamorphism degrees and various proportions of sulfide minerals. In the rock, sulfide minerals were often surrounded by a thin layer of carbonate minerals (siderite). Secondary reaction products observed in the damaged concrete include 'rust' mineral forms (e.g. ferric oxyhydroxides such as goethite, limonite (FeO (OH) nH{sub 2}O) and ferrihydrite), gypsum, ettringite and thaumasite. In the presence of water and oxygen, pyrrhotite oxidizes to form iron oxyhydroxides and sulphuric acid. The acid then reacts with the phases of the cement paste/aggregate and provokes the formation of sulfate minerals. Understanding both mechanisms, oxidation and internal sulfate attack, is important to be able to duplicate the damaging reaction in laboratory conditions, thus allowing the development of a performance test for evaluating the potential for deleterious expansion in concrete associated with sulfide-bearing aggregates.

Rodrigues, A. [Centre de Recherche sur les Infrastructures en Beton (CRIB), Universite Laval, 1065 ave de la Medecine, Quebec, QC, Canada G1V 0A6 (Canada)] [Centre de Recherche sur les Infrastructures en Beton (CRIB), Universite Laval, 1065 ave de la Medecine, Quebec, QC, Canada G1V 0A6 (Canada); Duchesne, J., E-mail: josee.duchesne@ggl.ulaval.ca [Centre de Recherche sur les Infrastructures en Beton (CRIB), Universite Laval, 1065 ave de la Medecine, Quebec, QC, Canada G1V 0A6 (Canada); Fournier, B. [Centre de Recherche sur les Infrastructures en Beton (CRIB), Universite Laval, 1065 ave de la Medecine, Quebec, QC, Canada G1V 0A6 (Canada)] [Centre de Recherche sur les Infrastructures en Beton (CRIB), Universite Laval, 1065 ave de la Medecine, Quebec, QC, Canada G1V 0A6 (Canada); Durand, B. [Institut de recherche d'Hydro-Quebec (IREQ), 1740 boul. Lionel-Boulet, Varennes, QC, Canada J3X 1S1 (Canada)] [Institut de recherche d'Hydro-Quebec (IREQ), 1740 boul. Lionel-Boulet, Varennes, QC, Canada J3X 1S1 (Canada); Rivard, P. [Universite de Sherbrooke, Sherbrooke, QC, Canada J1K 2R1 (Canada)] [Universite de Sherbrooke, Sherbrooke, QC, Canada J1K 2R1 (Canada); Shehata, M. [Ryerson University, 350 Victoria Street, Toronto, ON, Canada M5B 2K3 (Canada)] [Ryerson University, 350 Victoria Street, Toronto, ON, Canada M5B 2K3 (Canada)

2012-10-15

20

Binary counting with chemical reactions.  

PubMed

This paper describes a scheme for implementing a binary counter with chemical reactions. The value of the counter is encoded by logical values of "0" and "1" that correspond to the absence and presence of specific molecular types, respectively. It is incremented when molecules of a trigger type are injected. Synchronization is achieved with reactions that produce a sustained three-phase oscillation. This oscillation plays a role analogous to a clock signal in digital electronics. Quantities are transferred between molecular types in different phases of the oscillation. Unlike all previous schemes for chemical computation, this scheme is dependent only on coarse rate categories for the reactions ("fast" and "slow"). Given such categories, the computation is exact and independent of the specific reaction rates. Although conceptual for the time being, the methodology has potential applications in domains of synthetic biology such as biochemical sensing and drug delivery. We are exploring DNA-based computation via strand displacement as a possible experimental chassis. PMID:21121058

Kharam, Aleksandra; Jiang, Hua; Riedel, Marc; Parhi, Keshab

2011-01-01

21

Visualization of chemical reaction dynamics: Toward understanding complex polyatomic reactions  

PubMed Central

Polyatomic molecules have several electronic states that have similar energies. Consequently, their chemical dynamics often involve nonadiabatic transitions between multiple potential energy surfaces. Elucidating the complex reactions of polyatomic molecules is one of the most important tasks of theoretical and experimental studies of chemical dynamics. This paper describes our recent experimental studies of the multidimensional multisurface dynamics of polyatomic molecules based on two-dimensional ion/electron imaging. It also discusses ultrafast photoelectron spectroscopy of liquids for elucidating nonadiabatic electronic dynamics in aqueous solutions. PMID:23318678

SUZUKI, Toshinori

2013-01-01

22

Theoretical studies of chemical reaction dynamics  

SciTech Connect

This collaborative program with the Theoretical Chemistry Group at Argonne involves theoretical studies of gas phase chemical reactions and related energy transfer and photodissociation processes. Many of the reactions studied are of direct relevance to combustion; others are selected they provide important examples of special dynamical processes, or are of relevance to experimental measurements. Both classical trajectory and quantum reactive scattering methods are used for these studies, and the types of information determined range from thermal rate constants to state to state differential cross sections.

Schatz, G.C. [Argonne National Laboratory, IL (United States)

1993-12-01

23

Determining Interconnections in Chemical Reaction Networks Antonis Papachristodoulou and Ben Recht  

E-print Network

functionality in the neighborhood of the nominal reaction rates. But most importantly, networks are rarelyDetermining Interconnections in Chemical Reaction Networks Antonis Papachristodoulou and Ben Recht Abstract-- We present a methodology for robust determina- tion of chemical reaction network

Nowak, Robert

24

Plasmon-driven sequential chemical reactions in an aqueous environment  

PubMed Central

Plasmon-driven sequential chemical reactions were successfully realized in an aqueous environment. In an electrochemical environment, sequential chemical reactions were driven by an applied potential and laser irradiation. Furthermore, the rate of the chemical reaction was controlled via pH, which provides indirect evidence that the hot electrons generated from plasmon decay play an important role in plasmon-driven chemical reactions. In acidic conditions, the hot electrons were captured by the abundant H+ in the aqueous environment, which prevented the chemical reaction. The developed plasmon-driven chemical reactions in an aqueous environment will significantly expand the applications of plasmon chemistry and may provide a promising avenue for green chemistry using plasmon catalysis in aqueous environments under irradiation by sunlight. PMID:24958029

Zhang, Xin; Wang, Peijie; Zhang, Zhenglong; Fang, Yurui; Sun, Mengtao

2014-01-01

25

Dynamic Reaction Figures: An Integrative Vehicle for Understanding Chemical Reactions  

ERIC Educational Resources Information Center

A highly flexible learning tool, referred to as a dynamic reaction figure, is described. Application of these figures can (i) yield the correct chemical equation by simply following a set of menu driven directions; (ii) present the underlying "mechanism" in chemical reactions; and (iii) help to solve quantitative problems in a number of different…

Schultz, Emeric

2008-01-01

26

Classes of Chemical Reactions Reactions in aqueous media  

E-print Network

acid, HBr Phosphoric acid, H3PO4 Hydroiodic acid, HI Acetic acid, CH3CO2H Nitric acid, HNO3 CarbonicClasses of Chemical Reactions Reactions in aqueous media · Precipitation reactions · Acid + electrolytes: a substance that conducts an electric current when dissolved in water Acids are donors of H

Zakarian, Armen

27

2005 Chemical Reactions at Surfaces  

SciTech Connect

The Gordon Research Conference (GRC) on 2005 Chemical Reactions at Surfaces was held at Ventura Beach Marriott, Ventura California from February 13, 2005 through February 18, 2005. The Conference was well-attended with 124 participants (attendees list attached). The attendees represented the spectrum of endeavor in this field coming from academia, industry, and government laboratories, both U.S. and foreign scientists, senior researchers, young investigators, and students. In designing the formal speakers program, emphasis was placed on current unpublished research and discussion of the future target areas in this field. There was a conscious effort to stimulate lively discussion about the key issues in the field today. Time for formal presentations was limited in the interest of group discussions. In order that more scientists could communicate their most recent results, poster presentation time was scheduled. Attached is a copy of the formal schedule and speaker program and the poster program. In addition to these formal interactions, 'free time' was scheduled to allow informal discussions. Such discussions are fostering new collaborations and joint efforts in the field.

Cynthia M. Friend

2006-03-14

28

Microfabricated electrochemiluminescence cell for chemical reaction detection  

DOEpatents

A detector cell for a silicon-based or non-silicon-based sleeve type chemical reaction chamber that combines heaters, such as doped polysilicon for heating, and bulk silicon for convection cooling. The detector cell is an electrochemiluminescence cell constructed of layers of silicon with a cover layer of glass, with spaced electrodes located intermediate various layers forming the cell. The cell includes a cavity formed therein and fluid inlets for directing reaction fluid therein. The reaction chamber and detector cell may be utilized in any chemical reaction system for synthesis or processing of organic, inorganic, or biochemical reactions, such as the polymerase chain reaction (PCR) and/or other DNA reactions, such as the ligase chain reaction, which are examples of a synthetic, thermal-cycling-based reaction. The ECL cell may also be used in synthesis instruments, particularly those for DNA amplification and synthesis.

Northrup, M. Allen (Berkeley, CA); Hsueh, Yun-Tai (Davis, CA); Smith, Rosemary L. (Davis, CA)

2003-01-01

29

Chemical Kinetics: Rate of Reaction  

NSDL National Science Digital Library

This site offers an interactive tutorial that emphasizes graphical interpretation of chemical kinetics. The stoichiometric coefficients for a chemical equation are determined by comparing the slopes of concentration-time plots for the reactants and products. This tutorial is coupled to others to further guide the student to a better understanding of chemical kinetics.

Blauch, David N.

30

40 CFR 707.20 - Chemical substances import policy.  

...2014-07-01 2014-07-01 false Chemical substances import policy. 707.20...CONTINUED) TOXIC SUBSTANCES CONTROL ACT CHEMICAL IMPORTS AND EXPORTS General Import Requirements and Restrictions § 707.20 Chemical substances import policy. (a)...

2014-07-01

31

40 CFR 707.20 - Chemical substances import policy.  

Code of Federal Regulations, 2011 CFR

...2011-07-01 2011-07-01 false Chemical substances import policy. 707.20...CONTINUED) TOXIC SUBSTANCES CONTROL ACT CHEMICAL IMPORTS AND EXPORTS General Import Requirements and Restrictions § 707.20 Chemical substances import policy. (a)...

2011-07-01

32

40 CFR 707.20 - Chemical substances import policy.  

Code of Federal Regulations, 2013 CFR

...2013-07-01 2013-07-01 false Chemical substances import policy. 707.20...CONTINUED) TOXIC SUBSTANCES CONTROL ACT CHEMICAL IMPORTS AND EXPORTS General Import Requirements and Restrictions § 707.20 Chemical substances import policy. (a)...

2013-07-01

33

40 CFR 707.20 - Chemical substances import policy.  

Code of Federal Regulations, 2012 CFR

...2012-07-01 2012-07-01 false Chemical substances import policy. 707.20...CONTINUED) TOXIC SUBSTANCES CONTROL ACT CHEMICAL IMPORTS AND EXPORTS General Import Requirements and Restrictions § 707.20 Chemical substances import policy. (a)...

2012-07-01

34

40 CFR 707.20 - Chemical substances import policy.  

Code of Federal Regulations, 2010 CFR

...2010-07-01 2010-07-01 false Chemical substances import policy. 707.20...CONTINUED) TOXIC SUBSTANCES CONTROL ACT CHEMICAL IMPORTS AND EXPORTS General Import Requirements and Restrictions § 707.20 Chemical substances import policy. (a)...

2010-07-01

35

Controlling chemical reactions of a single particle  

NASA Astrophysics Data System (ADS)

Traditionally, chemical reactions have been investigated by tuning thermodynamic parameters, such as temperature or pressure. More recently, laser or magnetic field control methods have emerged to provide new experimental possibilities, in particular in the realm of cold collisions. The control of reaction pathways is also a critical component to implement molecular quantum information processing. For these studies, single particles provide a clean and well-controlled experimental system. Here, we report on the experimental tuning of the exchange reaction rates of a single trapped ion with ultracold neutral atoms by exerting control over both their quantum states. We observe the influence of the hyperfine interaction on chemical reaction rates and branching ratios, and monitor the kinematics of the reaction products. These investigations advance chemistry with single trapped particles towards achieving quantum-limited control of chemical reactions and indicate limits for buffer-gas cooling of single-ion clocks.

Ratschbacher, Lothar; Zipkes, Christoph; Sias, Carlo; Köhl, Michael

2012-09-01

36

Kinetic studies of elementary chemical reactions  

SciTech Connect

This program concerning kinetic studies of elementary chemical reactions is presently focussed on understanding reactions of NH{sub x} species. To reach this goal, the author is pursuing experimental studies of reaction rate coefficients and product branching fractions as well as using electronic structure calculations to calculate transition state properties and reaction rate calculations to relate these properties to predicted kinetic behavior. The synergy existing between the experimental and theoretical studies allow one to gain a deeper insight into more complex elementary reactions.

Durant, J.L. Jr. [Sandia National Laboratories, Livermore, CA (United States)

1993-12-01

37

Chemical Principles Revisited: Annotating Reaction Equations.  

ERIC Educational Resources Information Center

Urges chemistry teachers to have students annotate the chemical reactions in aqueous-solutions that they see in their textbooks and witness in the laboratory. Suggests this will help students recognize the reaction type more readily. Examples are given for gas formation, precipitate formation, redox interaction, acid-base interaction, and…

Tykodi, R. J.

1987-01-01

38

Quantum Chemical Approach to Estimating the Thermodynamics of Metabolic Reactions  

NASA Astrophysics Data System (ADS)

Thermodynamics plays an increasingly important role in modeling and engineering metabolism. We present the first nonempirical computational method for estimating standard Gibbs reaction energies of metabolic reactions based on quantum chemistry, which can help fill in the gaps in the existing thermodynamic data. When applied to a test set of reactions from core metabolism, the quantum chemical approach is comparable in accuracy to group contribution methods for isomerization and group transfer reactions and for reactions not including multiply charged anions. The errors in standard Gibbs reaction energy estimates are correlated with the charges of the participating molecules. The quantum chemical approach is amenable to systematic improvements and holds potential for providing thermodynamic data for all of metabolism.

Jinich, Adrian; Rappoport, Dmitrij; Dunn, Ian; Sanchez-Lengeling, Benjamin; Olivares-Amaya, Roberto; Noor, Elad; Even, Arren Bar; Aspuru-Guzik, Alán

2014-11-01

39

Quantum chemical approach to estimating the thermodynamics of metabolic reactions.  

PubMed

Thermodynamics plays an increasingly important role in modeling and engineering metabolism. We present the first nonempirical computational method for estimating standard Gibbs reaction energies of metabolic reactions based on quantum chemistry, which can help fill in the gaps in the existing thermodynamic data. When applied to a test set of reactions from core metabolism, the quantum chemical approach is comparable in accuracy to group contribution methods for isomerization and group transfer reactions and for reactions not including multiply charged anions. The errors in standard Gibbs reaction energy estimates are correlated with the charges of the participating molecules. The quantum chemical approach is amenable to systematic improvements and holds potential for providing thermodynamic data for all of metabolism. PMID:25387603

Jinich, Adrian; Rappoport, Dmitrij; Dunn, Ian; Sanchez-Lengeling, Benjamin; Olivares-Amaya, Roberto; Noor, Elad; Even, Arren Bar; Aspuru-Guzik, Alán

2014-01-01

40

Chemical Reactions in Supercritical Carbon Dioxide  

NASA Astrophysics Data System (ADS)

Utilizing supercritical fluids as environmentally benign solvents for chemical synthesis is one of the new approaches in the "greening" of chemistry. Carbon dioxide is the most widely used gas for supercritical fluid studies because of its moderate critical constants, nontoxic nature, and availability in pure form. One unique property of supercritical carbon dioxide (sc-CO2) is its high solubility for fluorinated compounds. Thus sc-CO2 can be used to replace Freons that are conventionally used as solvents for synthesis of perfluoro-polymers. Another property of sc-CO2 is its miscibility with gases such as H2. Heterogeneous reactions involving these gases may become homogeneous reactions in sc-CO2. Reactions in sc-CO2 may offer several advantages including controlling phase behavior and products, increasing speed of reactions, and obtaining specific reaction channels. This paper describes the following nine types of chemical reactions reported in the literature utilizing sc-CO2 as a solvent to illustrate the unique properties of the supercritical fluid reaction systems: (i) hydrogenation and hydroformylation, (ii) synthesis of organometallic compounds, (iii) metal chelation and extraction, (iv) preparation of inorganic nanoparticles, (v) stereo-selectivity of lipase-catalyzed reactions, (vi) asymmetric catalytic hydrogenation, (vii) polymerization, (viii) Diels-Alder reaction, and (ix) free radical reactions.

Wai, Chien M.; Hunt, Fred; Ji, Min; Chen, Xiaoyuan

1998-12-01

41

40 CFR 799.19 - Chemical imports and exports.  

Code of Federal Regulations, 2013 CFR

...2013-07-01 2013-07-01 false Chemical imports and exports. 799.19 Section...CONTINUED) IDENTIFICATION OF SPECIFIC CHEMICAL SUBSTANCE AND MIXTURE TESTING REQUIREMENTS General Provisions § 799.19 Chemical imports and exports. Persons...

2013-07-01

42

40 CFR 799.19 - Chemical imports and exports.  

...2014-07-01 2014-07-01 false Chemical imports and exports. 799.19 Section...CONTINUED) IDENTIFICATION OF SPECIFIC CHEMICAL SUBSTANCE AND MIXTURE TESTING REQUIREMENTS General Provisions § 799.19 Chemical imports and exports. Persons...

2014-07-01

43

40 CFR 799.19 - Chemical imports and exports.  

Code of Federal Regulations, 2010 CFR

...2010-07-01 2010-07-01 true Chemical imports and exports. 799.19 Section...CONTINUED) IDENTIFICATION OF SPECIFIC CHEMICAL SUBSTANCE AND MIXTURE TESTING REQUIREMENTS General Provisions § 799.19 Chemical imports and exports. Persons...

2010-07-01

44

40 CFR 799.19 - Chemical imports and exports.  

Code of Federal Regulations, 2011 CFR

...2011-07-01 2011-07-01 false Chemical imports and exports. 799.19 Section...CONTINUED) IDENTIFICATION OF SPECIFIC CHEMICAL SUBSTANCE AND MIXTURE TESTING REQUIREMENTS General Provisions § 799.19 Chemical imports and exports. Persons...

2011-07-01

45

40 CFR 799.19 - Chemical imports and exports.  

Code of Federal Regulations, 2012 CFR

...2012-07-01 2012-07-01 false Chemical imports and exports. 799.19 Section...CONTINUED) IDENTIFICATION OF SPECIFIC CHEMICAL SUBSTANCE AND MIXTURE TESTING REQUIREMENTS General Provisions § 799.19 Chemical imports and exports. Persons...

2012-07-01

46

Acceleration of chemical reaction by chaotic mixing  

E-print Network

Theory of fast binary chemical reaction, ${\\cal A}+{\\cal B}\\to{\\cal C}$, in a statistically stationary chaotic flow at large Schmidt number ${Sc}$ and large Damk\\"ohler number ${Da}$ is developed. For stoichiometric condition we identify subsequent stages of the chemical reaction. The first stage corresponds to the exponential decay, $\\propto\\exp(-\\lambda t)$ (where $\\lambda$ is the Lyapunov exponent of the flow), of the chemicals in the bulk part of the flow. The second and the third stages are related to the chemicals remaining in the boundary region. During the second stage the amounts of ${\\cal A}$ and ${\\cal B}$ decay $\\propto 1/\\sqrt{t}$, whereas the decay law during the third stage is exponential, $\\propto\\exp(-\\gamma t)$, where $\\gamma\\sim\\lambda/\\sqrt{Sc}$.

M. Chertkov; V. Lebedev

2003-01-27

47

Chemical memory reactions induced bursting dynamics in gene expression.  

PubMed

Memory is a ubiquitous phenomenon in biological systems in which the present system state is not entirely determined by the current conditions but also depends on the time evolutionary path of the system. Specifically, many memorial phenomena are characterized by chemical memory reactions that may fire under particular system conditions. These conditional chemical reactions contradict to the extant stochastic approaches for modeling chemical kinetics and have increasingly posed significant challenges to mathematical modeling and computer simulation. To tackle the challenge, I proposed a novel theory consisting of the memory chemical master equations and memory stochastic simulation algorithm. A stochastic model for single-gene expression was proposed to illustrate the key function of memory reactions in inducing bursting dynamics of gene expression that has been observed in experiments recently. The importance of memory reactions has been further validated by the stochastic model of the p53-MDM2 core module. Simulations showed that memory reactions is a major mechanism for realizing both sustained oscillations of p53 protein numbers in single cells and damped oscillations over a population of cells. These successful applications of the memory modeling framework suggested that this innovative theory is an effective and powerful tool to study memory process and conditional chemical reactions in a wide range of complex biological systems. PMID:23349679

Tian, Tianhai

2013-01-01

48

Laser enhanced chemical reaction studies  

NASA Astrophysics Data System (ADS)

The relaxation of vibrationally excited pyrazine (E = 40,640/cm) by collisions which populate the high J tail (J = 58-82) of the vibrationless ground state (00(exp 0)0) of CO2 has been studied using tunable infrared diode lasers to probe the scattered CO2 molecules. The nascent rotational populations and translational recoil velocities for a series of rotational states in the high J tail of the 00(exp 0)0 level of CO2 were measured at five collision cell temperatures: 243, 263, 298, 339, and 364 K. Both the rate constants describing these V-R/T processes and the translational temperatures describing the recoiling CO2 molecules exhibit a very weak positive temperature dependence indicating that the high energy CO2 molecules must originate from near the center of the pre-collision energy distribution. Quantitative estimates of the actual amount of energy transferred in collisions between CO2 and vibrationally excited pyrazine, based on an angular momentum and translational energy exponential gap model of the cross section, indicate that delta E(total) can be as large as 7090/cm (approximately 20 kcal/mol). These experiments offer compelling evidence that these energy transfer events can indeed be classified as supercollisions since they involve unusually large, single collision energy transfer magnitudes; and despite their relative infrequency, they play a most important role in the collisional deactivation of vibrationally excited pyrazine by a CO2 bath.

49

Classification of Chemical Reactions: Stages of Expertise  

ERIC Educational Resources Information Center

In this study we explore the strategies that undergraduate and graduate chemistry students use when engaged in classification tasks involving symbolic and microscopic (particulate) representations of different chemical reactions. We were specifically interested in characterizing the basic features to which students pay attention when classifying…

Stains, Marilyne; Talanquer, Vicente

2008-01-01

50

Laboratory Studies of Heterogeneous Chemical Processes of Atmospheric Importance  

NASA Technical Reports Server (NTRS)

The objective of this study is to conduct measurements of chemical kinetics parameters for heterogeneous reactions of importance in the stratosphere and the troposphere. It involves the elucidation of the mechanism of the interaction of HC1 vapor with ice surfaces, which is the first step in the heterogeneous chlorine activation processes, as well as the investigation of the atmospheric oxidation mechanism of soot particles emitted by biomass and fossil fuels. The techniques being employed include turbulent flow- chemical ionization mass spectrometry and optical ellipsometry, among others. The next section summarizes our research activities during the first year of the project, and the section that follows consists of the statement of work for the second year.

Molina, Mario J.

2003-01-01

51

Chemical reactions in reverse micelle systems  

DOEpatents

This invention is directed to conducting chemical reactions in reverse micelle or microemulsion systems comprising a substantially discontinuous phase including a polar fluid, typically an aqueous fluid, and a microemulsion promoter, typically a surfactant, for facilitating the formation of reverse micelles in the system. The system further includes a substantially continuous phase including a non-polar or low-polarity fluid material which is a gas under standard temperature and pressure and has a critical density, and which is generally a water-insoluble fluid in a near critical or supercritical state. Thus, the microemulsion system is maintained at a pressure and temperature such that the density of the non-polar or low-polarity fluid exceeds the critical density thereof. The method of carrying out chemical reactions generally comprises forming a first reverse micelle system including an aqueous fluid including reverse micelles in a water-insoluble fluid in the supercritical state. Then, a first reactant is introduced into the first reverse micelle system, and a chemical reaction is carried out with the first reactant to form a reaction product. In general, the first reactant can be incorporated into, and the product formed in, the reverse micelles. A second reactant can also be incorporated in the first reverse micelle system which is capable of reacting with the first reactant to form a product.

Matson, Dean W. (Kennewick, WA); Fulton, John L. (Richland, WA); Smith, Richard D. (Richland, WA); Consani, Keith A. (Richland, WA)

1993-08-24

52

Researches on Preliminary Chemical Reactions in Spark-Ignition Engines  

NASA Technical Reports Server (NTRS)

Chemical reactions can demonstrably occur in a fuel-air mixture compressed in the working cylinder of an Otto-cycle (spark ignition) internal-combustion engine even before the charge is ignited by the flame proceeding from the sparking plug. These are the so-called "prelinminary reactions" ("pre-flame" combustion or oxidation), and an exact knowledge of their characteristic development is of great importance for a correct appreciation of the phenomena of engine-knock (detonation), and consequently for its avoidance. Such reactions can be studied either in a working engine cylinder or in a combustion bomb. The first method necessitates a complicated experimental technique, while the second has the disadvantage of enabling only a single reaction to be studied at one time. Consequently, a new series of experiments was inaugurated, conducted in a motored (externally-driven) experimental engine of mixture-compression type, without ignition, the resulting preliminary reactions being detectable and measurable thermometrically.

Muehlner, E.

1943-01-01

53

Excited state quenching via "unsuccessful" chemical reactions.  

PubMed

We discuss the results of recent photochemical reaction path computations on 1n,pi* azoalkanes interacting with a single quencher molecule. We provide computational and experimental evidence that there are two basic mechanisms for the true quenching of 1n,pi* states both based on unsuccessful chemical reactions. The first mechanism is based upon an unsuccessful hydrogen atom transfer and may occur through two different (direct and stepwise) routes. The second mechanism is based on an unsuccessful charge transfer reaction that occurs exclusively in a direct fashion. We show that the efficiency of the two quenching mechanisms is substantially due to the existence of two different types of conical intersections between the excited and ground state potential energy surfaces of the reacting bimolecular system. PMID:12659494

Sinicropi, Adalgisa; Nau, Werner M; Olivucci, Massimo

2002-08-01

54

Mass Spectroscopy of Chemical Reaction of 3d Metal Clusters Involved in Chemical Vapor Deposition Synthesis of Carbon Nanotubes  

Microsoft Academic Search

The chemical reactions of transition metal clusters in the gas phase have aroused considerable scientific interest and are also of critical scientific importance. For example, these reactions are involved in the synthesis of single-walled carbon nanotubes, which are considered ideal materials because of their outstanding properties. Alcohol catalytic chemical vapor deposition (ACCVD) is one of the best synthetic processes for

Shuhei Inoue; Shigeo Maruyama

2008-01-01

55

Reduction of Chemical Reactions in Nitrogen and Nitrogen–Hydrogen Plasma Jets Flowing into Atmospheric Air  

Microsoft Academic Search

The large number of possible chemical reactions represents a severe burdenfor modeling of even relatively simple plasma systems. Reduced sets ofchemical reactions have been obtained for numerical simulations of nitrogenand nitrogen-hydrogen plasma jets flowing into an atmospheric airenvironment. The important or active reactions are determined based on asimplified reduction method. A reaction is considered active if it leadsto higher sensitivities

J. H. Park; E. Pfender; C. H. Chang

2000-01-01

56

Assessing the importance of proton transfer reactions in DNA.  

PubMed

Although engineered by millions of years of evolution, the cellular machinery is not flawless, and errors regularly appear during DNA replication. The subsequent alteration of the stored genetic message results in a mutation and might be the starting point of important health disorders. The question therefore is what causes DNA mutations? All living organisms are constantly exposed to a number of external agents such as free radicals and to radiation, which may lead to induced mutations. There are also mutations happening without invoking the action of any exogenous element, the so-called spontaneous mutations. The former can be partially controlled by avoiding exposure to high-risk environments, while the latter are more intriguing because their origin is unclear and difficult to determine. As noted by Watson and Crick when they first discovered the DNA structure, the correct replication of DNA rests on the assumption that the base pairs remain in their most stable, canonical form. However, protons along the interbase hydrogen-bond network are not static entities. They can in fact interchange their positions in DNA bases through proton transfer (PT) reactions before strands unwind, giving rise to noncanonical structures defined as rare tautomers. The importance of these rare tautomers was also cleverly anticipated by Watson and Crick and some years later claimed by Löwdin to be a source of spontaneous mutations. In Watson and Crick's words: "It would be of interest to know the precise difference in free energy between the various tautomeric forms under physiological conditions." Unfortunately, rare tautomeric forms are very difficult to detect, so no direct and accurate free energy measure has been discerned. In contrast, theoretical chemistry is making good progress toward the quantification of PT reactions in DNA and their biological consequences. This Account touches upon the theoretical studies devoted to appraising the importance of rare tautomers as promoters of spontaneous mutations. We focus in particular on the crucial role played by the biological environment on DNA stability. It has now been demonstrated that valuable macroscopic predictions require not only highly accurate theories but also refined chemical models. Hybrid quantum mechanics/molecular mechanics (QM/MM) simulations performed on short but complete DNA sequence fragments emerge in this context as the most adequate tools. In addition, these methods can be used to quantify the effect of different external agents on the PT tautomeric equilibria and, eventually, to conveniently handle them. This is the case for the possible alteration of the naturally observed mutation rate by exposure to intense electric fields. Theoretical predictions envision in this respect promising applications of ultrashort electric pulses in medicine to selectively modify the mutated/canonical ratio in DNA. PMID:24849375

Jacquemin, Denis; Zúñiga, José; Requena, Alberto; Céron-Carrasco, José Pedro

2014-08-19

57

The role of chemical reactions in the Chernobyl accident  

SciTech Connect

It is shown that chemical reactions played an essential role in the Chernobyl accident at all of its stages. It is important that the reactor before the explosion was at maximal xenon poisoning, and its reactivity, apparently, was not destroyed by the explosion. The reactivity release due to decay of Xe-235 on the second day after the explosion led to a reactor power of 80-110 MW. Owing to this power, the chemical reactions of reduction of uranium, plutonium, and other metals at a temperature of about 2000 Degree-Sign C occurred in the core. The yield of fission products thus sharply increased. Uranium and other metals flew down in the bottom water communications and rooms. After reduction of the uranium and its separation from the graphite, the chain reaction stopped, the temperature of the core decreased, and the activity yield stopped.

Grishanin, E. I., E-mail: egrishanin@orexovo.net [Russian Research Center Kurchatov Institute (Russian Federation)

2010-12-15

58

Multiscale stochastic simulations of chemical reactions with regulated scale separation  

SciTech Connect

We present a coupling of multiscale frameworks with accelerated stochastic simulation algorithms for systems of chemical reactions with disparate propensities. The algorithms regulate the propensities of the fast and slow reactions of the system, using alternating micro and macro sub-steps simulated with accelerated algorithms such as ? and R-leaping. The proposed algorithms are shown to provide significant speedups in simulations of stiff systems of chemical reactions with a trade-off in accuracy as controlled by a regulating parameter. More importantly, the error of the methods exhibits a cutoff phenomenon that allows for optimal parameter choices. Numerical experiments demonstrate that hybrid algorithms involving accelerated stochastic simulations can be, in certain cases, more accurate while faster, than their corresponding stochastic simulation algorithm counterparts.

Koumoutsakos, Petros, E-mail: petros@ethz.ch [Chair of Computational Science, Clausiusstrasse 33, ETH Zurich, CH-8092 (Switzerland)] [Chair of Computational Science, Clausiusstrasse 33, ETH Zurich, CH-8092 (Switzerland); Feigelman, Justin [Chair of Computational Science, Clausiusstrasse 33, ETH Zurich, CH-8092 (Switzerland)] [Chair of Computational Science, Clausiusstrasse 33, ETH Zurich, CH-8092 (Switzerland)

2013-07-01

59

Molecular Dynamics Simulations of Chemical Reactions for Use in Education  

ERIC Educational Resources Information Center

One of the simulation engines of an open-source program called the Molecular Workbench, which can simulate thermodynamics of chemical reactions, is described. This type of real-time, interactive simulation and visualization of chemical reactions at the atomic scale could help students understand the connections between chemical reaction equations…

Qian Xie; Tinker, Robert

2006-01-01

60

Chemical Reaction due to Stronger Ramachandran Interaction  

E-print Network

The origin of a chemical reaction between two reactant atoms is associated to the activation energy, with the assumption that, high-energy collisions between these atoms, are the ones that overcome the activation energy. Here, we (i) show that a stronger attractive van der Waals (vdW) and electron-ion Coulomb interactions between two polarized atoms are responsible to initiate a chemical reaction, either before or after the collision. We derive this stronger vdW attraction formula exactly using the quasi one-dimensional Drude model within the ionization energy theory and the energy-level spacing renormalization group method. Along the way, we (ii) expose the precise physical mechanism responsible for the existence of a stronger vdW interaction for both long and short distances, and also show how to technically avoid the electron-electron Coulomb repulsion between polarized electrons from these two reactant atoms. Finally, we properly and correctly associate the existence of this stronger attraction to Ramachandran's 'normal limits' (distance shorter than what is allowed by the standard vdW bond) between chemically nonbonded atoms.

Andrew Das Arulsamy

2011-10-15

61

A Synthetic Reaction Network: Chemical Amplification Using Nonequilibrium Autocatalytic Reactions Coupled in Time  

E-print Network

reaction network that performs a function: it uses autocatalysis in a time- controlled microfluidic device the reactions in space and time.1-5 An example of a chemical network is an array of 16 coupled reactionsA Synthetic Reaction Network: Chemical Amplification Using Nonequilibrium Autocatalytic Reactions

Ismagilov, Rustem F.

62

Chemical Looping Combustion Reactions and Systems  

SciTech Connect

Chemical Looping Combustion (CLC) is one promising fuel-combustion technology, which can facilitate economic CO{sub 2} capture in coal-fired power plants. It employs the oxidation/reduction characteristics of a metal, or oxygen carrier, and its oxide, the oxidizing gas (typically air) and the fuel source may be kept separate. This topical report discusses the results of four complementary efforts: (5.1) the development of process and economic models to optimize important design considerations, such as oxygen carrier circulation rate, temperature, residence time; (5.2) the development of high-performance simulation capabilities for fluidized beds and the collection, parameter identification, and preliminary verification/uncertainty quantification; (5.3) the exploration of operating characteristics in the laboratoryscale bubbling bed reactor, with a focus on the oxygen carrier performance, including reactivity, oxygen carrying capacity, attrition resistance, resistance to deactivation, cost and availability; and (5.4) the identification of kinetic data for copper-based oxygen carriers as well as the development and analysis of supported copper oxygen carrier material. Subtask 5.1 focused on the development of kinetic expressions for the Chemical Looping with Oxygen Uncoupling (CLOU) process and validating them with reported literature data. The kinetic expressions were incorporated into a process model for determination of reactor size and oxygen carrier circulation for the CLOU process using ASPEN PLUS. An ASPEN PLUS process model was also developed using literature data for the CLC process employing an iron-based oxygen carrier, and the results of the process model have been utilized to perform a relative economic comparison. In Subtask 5.2, the investigators studied the trade-off between modeling approaches and available simulations tools. They quantified uncertainty in the high-performance computing (HPC) simulation tools for CLC bed applications. Furthermore, they performed a sensitivity analysis for velocity, height and polydispersity and compared results against literature data for experimental studies of CLC beds with no reaction. Finally, they present an optimization space using simple non-reactive configurations. In Subtask 5.3, through a series of experimental studies, behavior of a variety of oxygen carriers with different loadings and manufacturing techniques was evaluated under both oxidizing and reducing conditions. The influences of temperature, degree of carrier conversion and thermodynamic driving force resulting from the difference between equilibrium and system O{sub 2} partial pressures were evaluated through several experimental campaigns, and generalized models accounting for these influences were developed to describe oxidation and oxygen release. Conversion of three solid fuels with widely ranging reactivities was studied in a small fluidized bed system, and all but the least reactive fuel (petcoke) were rapidly converted by oxygen liberated from the CLOU carrier. Attrition propensity of a variety of carriers was also studied, and the carriers produced by freeze granulation or impregnation of preformed substrates displayed the lowest rates of attrition. Subtask 5.4 focused on gathering kinetic data for a copper-based oxygen carrier to assist with modeling of a functioning chemical looping reactor. The kinetics team was also responsible for the development and analysis of supported copper oxygen carrier material.

Sarofim, Adel; Lighty, JoAnn; Smith, Philip; Whitty, Kevin; Eyring, Edward; Sahir, Asad; Alvarez, Milo; Hradisky, Michael; Clayton, Chris; Konya, Gabor; Baracki, Richard; Kelly, Kerry

2014-03-01

63

Continuous Time Markov Chain Models for Chemical Reaction  

E-print Network

Chapter 7 Continuous Time Markov Chain Models for Chemical Reaction Networks 7.1 Chemical reaction of the reactants and to the length of the time interval. In other words, since for the reaction to occur a molecule that is available at time t and is a positive constant, the reaction rate constant. Mathematically, Ft

Anderson, David F.

64

Some chemical and mineralogical considerations important for understanding leachate chemistry  

SciTech Connect

Both the raw shale material and the retorting process parameters are influential in determining the subsequent behavior of the spent shale solids with respect to leaching and/or environmental weathering. The process parameters define the mineral reactions that occur to form the mineral assemblage in the spent shale, while the major and trace element residences and mobilities from the raw shale determine the extent of incorporation of these elements in the spent shale matrix and ultimately the composition of leachate generated by the spent shale solid: water interaction. In order to understand leachate compositions, it is necessary to determine this water: solid interaction, but the solid wastes being considered are a dependent function of the raw shale material and the process parameters. Thus, in order to understand the chemical principles operative in leachate generation, it is necessary to elucidate the interplay of the raw material and the process parameters in the formation of the waste and then the interaction of the waste form with water. The leachate and the solid waste are dependent variables, while the raw shale and the process parameters are independent variables. These considerations are illustrated by results of chemical characterization and experimental studies of field generated spent shales. Results from field generated materials are used to describe important considerations relative to the understanding of leachate chemistry.

Peterson, E.J.; Wagner, P.

1982-01-01

65

Chemical reaction fouling model for single-phase heat transfer  

SciTech Connect

A fouling model was developed on the premise that the chemical reaction for generation of precursor can take place in the bulk fluid, in the thermalboundary layer, or at the fluid/wall interface, depending upon the interactive effects of flu id dynamics, heat and mass transfer, and the controlling chemical reaction. The analysis was used to examine the experimental data for fouling deposition of polyperoxides produced by autoxidation of indene in kerosene. The effects of fluid and wall temperatures for two flow geometries were analyzed. The results showed that the relative effects of physical parameters on the fouling rate would differ for the three fouling mechanisms; therefore, it is important to identify the controlling mechanism in applying the closed-flow-loop data to industrial conditions.

Panchal, C.B. [Argonne National Lab., IL (United States); Watkinson, A.P. [British Columbia Univ., Vancouver, BC (Canada)

1993-08-01

66

Silicon-based sleeve devices for chemical reactions  

DOEpatents

A silicon-based sleeve type chemical reaction chamber that combines heaters, such as doped polysilicon for heating, and bulk silicon for convection cooling. The reaction chamber combines a critical ratio of silicon and silicon nitride to the volume of material to be heated (e.g., a liquid) in order to provide uniform heating, yet low power requirements. The reaction chamber will also allow the introduction of a secondary tube (e.g., plastic) into the reaction sleeve that contains the reaction mixture thereby alleviating any potential materials incompatibility issues. The reaction chamber may be utilized in any chemical reaction system for synthesis or processing of organic, inorganic, or biochemical reactions, such as the polymerase chain reaction (PCR) and/or other DNA reactions, such as the ligase chain reaction, which are examples of a synthetic, thermal-cycling-based reaction. The reaction chamber may also be used in synthesis instruments, particularly those for DNA amplification and synthesis.

Northrup, M. Allen (Berkeley, CA); Mariella, Jr., Raymond P. (Danville, CA); Carrano, Anthony V. (Livermore, CA); Balch, Joseph W. (Livermore, CA)

1996-01-01

67

Chemical Reaction Dynamics accompanying Electron-Transfer Osamu SUGINO  

E-print Network

transfer as does in the redox, while the latter appears in the photochemical reactions. Simulating bothChemical Reaction Dynamics accompanying Electron-Transfer Osamu SUGINO Institute for Solid State Physics, the University of Tokyo 5-1-5 Kashiwanoha, Chiba 277-8581 1. Introduction Many chemical reactions

Katsumoto, Shingo

68

Thermodynamic performance for a chemical reactions model  

NASA Astrophysics Data System (ADS)

This paper presents the analysis efficiency of a chemical reaction model of four states, such that their activated states can occur at any point (fixed but arbitrary) of the transition from one state to another. This mechanism operates under a single heat reservoir temperature, unlike the internal combustion engines where there are two thermal sources. Different efficiencies are compared to this model, which operate at different optimum engine regimes. Thus, some analytical methods are used to give an approximate expression, facilitating the comparison between them. Finally, the result is compared with that obtained by other authors considered a general model of an isothermal molecular machine. Taking into account the above, the results seems to follow a similar behaviour for all the optimized engines, which resemble that observed in the case of heat engine efficiencies.

Gonzalez-Narvaez, R. E.; Sánchez-Salas, N.; Chimal-Eguía, J. C.

2015-01-01

69

Continuous time Markov chain models for chemical reaction networks  

E-print Network

Continuous time Markov chain models for chemical reaction networks David F. Anderson Departments for the model for the reaction is that the probability of the reaction occurring in a small time interval (t and to the length of the time interval. In other words, since for the reaction to occur a molecule

Kurtz, Tom

70

CONTINUOUS TIME MARKOV CHAIN MODELS FOR CHEMICAL REACTION NETWORKS  

E-print Network

Chapter 1 CONTINUOUS TIME MARKOV CHAIN MODELS FOR CHEMICAL REACTION NETWORKS David F. Anderson of identifying the different time scales and deriving the reduced models. Keywords: Reaction network, Markov for the reaction is that the probability of the reaction occurring in a small time inter- val (t, t + t] should

Anderson, David F.

71

Prediction and Prevention of Chemical Reaction Hazards: Learning by Simulation.  

ERIC Educational Resources Information Center

Points out that chemical hazards are the major cause of accidents in chemical industry and describes a safety teaching approach using a simulation. Explains a problem statement on exothermic liquid-phase reactions. (YDS)

Shacham, Mordechai; Brauner, Neima; Cutlip, Michael B.

2001-01-01

72

GREEN CHEMICAL SYNTHESIS THROUGH CATALYSIS AND ALTERNATE REACTION CONDITIONS  

EPA Science Inventory

Green chemical synthesis through catalysis and alternate reaction conditions Encompassing green chemistry techniques and methodologies, we have initiated several projects at the National Risk Management Research laboratory that focus on the design and development of chemic...

73

Crossed molecular beam studies of atmospheric chemical reaction dynamics  

SciTech Connect

The dynamics of several elementary chemical reactions that are important in atmospheric chemistry are investigated. The reactive scattering of ground state chlorine or bromine atoms with ozone molecules and ground state chlorine atoms with nitrogen dioxide molecules is studied using a crossed molecular beams apparatus with a rotatable mass spectrometer detector. The Cl + O{sub 3} {yields} ClO + O{sub 2} reaction has been studied at four collision energies ranging from 6 kcal/mole to 32 kcal/mole. The derived product center-of-mass angular and translational energy distributions show that the reaction has a direct reaction mechanism and that there is a strong repulsion on the exit channel. The ClO product is sideways and forward scattered with respect to the Cl atom, and the translational energy release is large. The Cl atom is most likely to attack the terminal oxygen atom of the ozone molecule. The Br + O{sub 3} {yields} ClO + O{sub 2} reaction has been studied at five collision energies ranging from 5 kcal/mole to 26 kcal/mole. The derived product center-of-mass angular and translational energy distributions are quite similar to those in the Cl + O{sub 3} reaction. The Br + O{sub 3} reaction has a direct reaction mechanism similar to that of the Cl + O{sub 3} reaction. The electronic structure of the ozone molecule seems to play the central role in determining the reaction mechanism in atomic radical reactions with the ozone molecule. The Cl + NO{sub 2} {yields} ClO + NO reaction has been studied at three collision energies ranging from 10.6 kcal/mole to 22.4 kcal/mole. The center-of-mass angular distribution has some forward-backward symmetry, and the product translational energy release is quite large. The reaction proceeds through a short-lived complex whose lifetime is less than one rotational period. The experimental results seem to show that the Cl atom mainly attacks the oxygen atom instead of the nitrogen atom of the NO{sub 2} molecule.

Zhang, Jingsong

1993-04-01

74

Direct Monte Carlo simulation of chemical reaction systems: Simple bimolecular reactions  

E-print Network

Direct Monte Carlo simulation of chemical reaction systems: Simple bimolecular reactions Shannon D and understanding the behavior of gas phase chemical reaction systems. This Monte Carlo method, originated by Bird useful, and the gas dynamics of many systems is more easily predicted and understood by using Monte Carlo

Anderson, James B.

75

Using chemical tracers in hillslope soils to estimate the importance of chemical denudation under  

E-print Network

Using chemical tracers in hillslope soils to estimate the importance of chemical denudation under mass. The model includes both sediment transport and chemical denudation. A simplified two-phase model is developed; the two phases are a chemically immobile phase, which has far lower solubility than the bulk soil

76

Flow Tube Studies of Gas Phase Chemical Processes of Atmospheric Importance  

NASA Technical Reports Server (NTRS)

The objective of this project is to conduct measurements of elementary reaction rate constants and photochemistry parameters for processes of importance in the atmosphere. These measurements are being carried out under temperature and pressure conditions covering those applicable to the stratosphere and upper troposphere, using the chemical ionization mass spectrometry turbulent flow technique developed in our laboratory.

Molina, Mario J.

1997-01-01

77

Chemical kinetics computer program for static and flow reactions  

NASA Technical Reports Server (NTRS)

General chemical kinetics computer program for complex gas mixtures has been developed. Program can be used for any homogeneous reaction in either one dimensional flow or static system. It is flexible, accurate, and easy to use. It can be used for any chemical system for which species thermodynamic data and reaction rate constant data are known.

Bittker, D. A.; Scullin, V. J.

1972-01-01

78

Students’ Microscopic, Macroscopic, and Symbolic Representations of Chemical Reactions  

Microsoft Academic Search

This study examined the mental representations of chemical reactions used by six students (three male, three female) who achieved above-average grades in a college freshman chemistry class at a large midwestern university. The representations expressed by the students in structured interviews were categorized as microscopic, macroscopic, or symbolic representations of chemical reactions. The study revealed that the participants did make

Michael E. Hinton; Mary B. Nakhleh

1999-01-01

79

Laboratory Studies of Homogeneous and Heterogeneous Chemical Processes of Importance in the Upper Atmosphere  

NASA Technical Reports Server (NTRS)

The objective of this study was to conduct measurements of chemical kinetics parameters for reactions of importance in the stratosphere and upper troposphere, and to study the interaction of trace gases with ice surfaces in order to elucidate the mechanism of heterogeneous chlorine activation processes, using both a theoretical and an experimental approach. The measurements were carried out under temperature and pressure conditions covering those applicable to the stratosphere and upper troposphere. The main experimental technique employed was turbulent flow-chemical ionization mass spectrometry, which is particularly well suited for investigations of radical-radical reactions.

Molina, Mario J.

2003-01-01

80

Advanced Chemical Heat Pumps Using Liquid-Vapor Reactions  

E-print Network

ADVANCED CHEMICAL HEAT PUMPS USING LIQUID-VAPOR REACTIONS LANCE KIROL Senior Program Specialist Idaho National Engineering Laboratory Idaho Falls, Idaho . ABSTRACT Chemical heat pumps utilizing liquid-vapor reactions can be configured... characteristics. A waste heat driven heat pump (temperature amplifier) using liquid-vapor chem1cal reactions- can oper ate with higher coefficient of performance and smaller heat exchangers than an absorption temp erature amplifying heat pump. Higher tempera...

Kirol, L.

81

Deterministic Function Computation with Chemical Reaction Networks*  

PubMed Central

Chemical reaction networks (CRNs) formally model chemistry in a well-mixed solution. CRNs are widely used to describe information processing occurring in natural cellular regulatory networks, and with upcoming advances in synthetic biology, CRNs are a promising language for the design of artificial molecular control circuitry. Nonetheless, despite the widespread use of CRNs in the natural sciences, the range of computational behaviors exhibited by CRNs is not well understood. CRNs have been shown to be efficiently Turing-universal (i.e., able to simulate arbitrary algorithms) when allowing for a small probability of error. CRNs that are guaranteed to converge on a correct answer, on the other hand, have been shown to decide only the semilinear predicates (a multi-dimensional generalization of “eventually periodic” sets). We introduce the notion of function, rather than predicate, computation by representing the output of a function f : ?k ? ?l by a count of some molecular species, i.e., if the CRN starts with x1, …, xk molecules of some “input” species X1, …, Xk, the CRN is guaranteed to converge to having f(x1, …, xk) molecules of the “output” species Y1, …, Yl. We show that a function f : ?k ? ?l is deterministically computed by a CRN if and only if its graph {(x, y) ? ?k × ?l ? f(x) = y} is a semilinear set. Finally, we show that each semilinear function f (a function whose graph is a semilinear set) can be computed by a CRN on input x in expected time O(polylog ?x?1). PMID:25383068

Chen, Ho-Lin; Doty, David; Soloveichik, David

2013-01-01

82

An Analysis of the Algebraic Method for Balancing Chemical Reactions.  

ERIC Educational Resources Information Center

Analyzes the algebraic method for balancing chemical reactions. Introduces a third general condition that involves a balance between the total amount of oxidation and reduction. Requires the specification of oxidation states for all elements throughout the reaction. Describes the general conditions, the mathematical treatment, redox reactions, and…

Olson, John A.

1997-01-01

83

Chemical Demonstrations with Consumer Chemicals: The Black and White Reaction.  

ERIC Educational Resources Information Center

Describes a dramatic chemical demonstration in which chemicals that are black and white combine to produce a colorless liquid. Reactants include tincture of iodine, bleach, white vinegar, Epsom salt, vitamin C tablets, and liquid laundry starch. (DDR)

Wright, Stephen W.

2002-01-01

84

Restricted cooperative games on metabolic networks reveal functionally important reactions.  

PubMed

Understanding the emerging properties of complex biological systems is in the crux of systems biology studies. Computational methods for elucidating the role of each component in the synergetic interplay can be used to identify targets for genetic and metabolic engineering. In particular, we aim at determining the importance of reactions in a metabolic network with respect to a specific biological function. Therefore, we propose a novel game-theoretic framework which integrates restricted cooperative games with the outcome of flux balance analysis. We define productivity games on metabolic networks and present an analysis of their unrestricted and restricted variants based on the game-theoretic solution concept of the Shapley value. Correspondingly, this concept provides a characterization of the robustness and functional centrality for each enzyme involved in a given metabolic network. Furthermore, the comparison of two different environments - feast and famine - demonstrates the dependence of the results on the imposed flux capacities. PMID:22940237

Sajitz-Hermstein, Max; Nikoloski, Zoran

2012-12-01

85

Morphological changes of amphiphilic molecular assemblies induced by chemical reactions.  

PubMed

Shape transformations of amphiphilic molecular assemblies induced by chemical reactions are studied using coarse-grained molecular simulations. A binding reaction between hydrophilic and hydrophobic molecules is considered. It is found that the reaction induces transformation of an oil droplet to a tubular vesicle via bicelles and vesicles with discoidal arms. The discoidal arms close into vesicles, which are subsequently fused into the tubular vesicle. Under the chemical reaction, the bicelle-to-vesicle transition occurs at smaller sizes than in the absence of the hydrophobic molecules. It is revealed that the enhancement of this transition is due to embedded hydrophobic particles that reduce the membrane bending rigidity. PMID:25582908

Nakagawa, Koh M; Noguchi, Hiroshi

2015-02-01

86

Non-equilibrium effects in high temperature chemical reactions  

NASA Technical Reports Server (NTRS)

Reaction rate data were collected for chemical reactions occurring at high temperatures during reentry of space vehicles. The principle of detailed balancing is used in modeling kinetics of chemical reactions at high temperatures. Although this principle does not hold for certain transient or incubation times in the initial phase of the reaction, it does seem to be valid for the rates of internal energy transitions that occur within molecules and atoms. That is, for every rate of transition within the internal energy states of atoms or molecules, there is an inverse rate that is related through an equilibrium expression involving the energy difference of the transition.

Johnson, Richard E.

1987-01-01

87

Morphological changes of amphiphilic molecular assemblies induced by chemical reaction  

E-print Network

Shape transformations of amphiphilic molecular assemblies induced by chemical reaction are studied using coarse-grained molecular simulations. A binding reaction between hydrophilic and hydrophobic molecules is considered. It is found that the reaction induces transformation of an oil droplet to a tubular vesicle via bicelles and vesicles with discoidal arms. The discoidal arms close into vesicles, which are subsequently fused into the tubular vesicle. Under the chemical reaction, the bicelle-to-vesicle transition occurs at smaller sizes than in the absence of the hydrophobic molecules. It is revealed that the enhancement of this transition is due to embedded hydrophobic particles that reduce the membrane bending rigidity.

Koh M. Nakagawa; Hiroshi Noguchi

2014-11-21

88

FACILITATED CHEMICAL SYNTHESIS UNDER ALTERNATE REACTION CONDITIONS  

EPA Science Inventory

The chemical research in the late 1990's witnessed a paradigm shift towards "environmentally-friendly chemistry" more popularly known as "green chemistry" due to the increasing environmental concerns and legislative requirements to curb the release of chemical waste into the atmo...

89

Chemical Master versus Chemical Langevin for First-Order Reaction Networks  

E-print Network

Chemical Master versus Chemical Langevin for First-Order Reaction Networks Desmond J. Higham Raya in computational cell biology, and in this case, the interactions are typically first-order. The Chemical Langevin effectively. In this work, we obtain expressions for the first and second moments of the Chemical Langevin

Mottram, Nigel

90

Kinetics of Chemical Reactions in Flames  

NASA Technical Reports Server (NTRS)

In part I of the paper the theory of flame propagation is developed along the lines followed by Frank-Kamenetsky and one of the writers. The development of chain processes in flames is considered. A basis is given for the application of the method of stationary concentrations to reactions in flames; reactions with branching chains are analyzed. The case of a diffusion coefficient different from the coefficient of temperature conductivity is considered.

Zeldovich, Y.; Semenov, N.

1946-01-01

91

Mass Accommodation and Chemical Reaction at Gas-Liquid Interfaces  

NASA Astrophysics Data System (ADS)

The uptake of trace gases by liquid surfaces is an important process that initiates the heterogeneous chemistry of liquid aerosol particles and cloud droplets. We have recently reviewed the available experimental data for liquid aqueous and aqueous/organic surfaces (1). The review highlights some inconsistencies among experimental results and between experimental results and molecular dynamics simulations. Some of these inconsistencies will be evaluated and discussed in terms of the physics of liquid interfaces, the limitations of various experimental techniques and the disparate scales of laboratory experiments and current molecular simulations (1, 2). 1. Davidovits, P., Kolb, C. E., Williams, L. R., Jayne, J. T., Worsnop, D. R., 2006, Mass Accommodation and Chemical Reactions at Gas Liquid Interfaces, Chem. Rev. 106, 1323-1354. 2. Garrett, B. C., Schenter, G. K., Morita, A., 2006, Molecular Simulations of Molecules across the Liquid/Vapor Interface of Water, Chem. Rev. 106, 1355-1374.

Kolb, C. E.; Williams, L. R.; Jayne, J. T.; Worsnop, D. R.; Davidovits, P.

2006-12-01

92

Understanding Chemical Reaction Kinetics and Equilibrium with Interlocking Building Blocks  

ERIC Educational Resources Information Center

Chemical reaction kinetics and equilibrium are essential core concepts of chemistry but are challenging topics for many students, both at the high school and undergraduate university level. Visualization at the molecular level is valuable to aid understanding of reaction kinetics and equilibrium. This activity provides a discovery-based method to…

Cloonan, Carrie A.; Nichol, Carolyn A.; Hutchinson, John S.

2011-01-01

93

Is the simplest chemical reaction really so simple?  

PubMed Central

Modern computational methods have become so powerful for predicting the outcome for the H + H2 ? H2 + H bimolecular exchange reaction that it might seem further experiments are not needed. Nevertheless, experiments have led the way to cause theorists to look more deeply into this simplest of all chemical reactions. The findings are less simple. PMID:24367084

Jankunas, Justin; Sneha, Mahima; Zare, Richard N.; Bouakline, Foudhil; Althorpe, Stuart C.; Herráez-Aguilar, Diego; Aoiz, F. Javier

2014-01-01

94

Elementary reaction modeling of solid oxide electrolysis cells: Main zones for heterogeneous chemical/electrochemical reactions  

NASA Astrophysics Data System (ADS)

A theoretical model of solid oxide electrolysis cells considering the heterogeneous elementary reactions, electrochemical reactions and the transport process of mass and charge is applied to study the relative performance of H2O electrolysis, CO2 electrolysis and CO2/H2O co-electrolysis and the competitive behavior of heterogeneous chemical and electrochemical reactions. In cathode, heterogeneous chemical reactions exist near the outside surface and the electrochemical reactions occur near the electrolyte. According to the mathematical analysis, the mass transfer flux D ?c determines the main zone size of heterogeneous chemical reactions, while the charge transfer flux ? ?V determines the other one. When the zone size of heterogeneous chemistry is enlarged, more CO2 could react through heterogeneous chemical pathway, and polarization curves of CO2/H2O co-electrolysis could be prone to H2O electrolysis. Meanwhile, when the zone size of electrochemistry is enlarged, more CO2 could react through electrochemical pathway, and polarization curves of CO2/H2O co-electrolysis could be prone to CO2 electrolysis. The relative polarization curves, the ratio of CO2 participating in electrolysis and heterogeneous chemical reactions, the mass and charge transfer flux and heterogeneous chemical/electrochemical reaction main zones are simulated to study the effects of cathode material characteristics (porosity, particle diameter and ionic conductivity) and operating conditions (gas composition and temperature).

Li, Wenying; Shi, Yixiang; Luo, Yu; Cai, Ningsheng

2015-01-01

95

Mineralization of hazardous chemicals by heme reaction  

SciTech Connect

The catalytic degradation of pentachlorophenol contaminated soil by heme and hydrogen peroxide has been reported. Here we studied evidence for the mechanism and mineralization by the heme catalyzed reaction for hazardous organopollutants. Ferryl heme radical and non-radical ferryl heme were generated rapidly by the interaction of heme and hydrogen peroxide (H{sub 2}O{sub 2}). The activated heme radical could initiate the oxidation of 5-aminosalicylic acid (5-ASA). The reactions by heme with H{sub 2}O{sub 2} could support the redox cycling between the ferryl species of heme and 5-ASA as the mechanistic routes of the heme catalyzed reaction. Hazardous compounds such as pentachlorophenol, phenanthrene and benzota[a]pyrene were mineralized 20, 6, and 7%, respectively, with 30 mM heme and 1500 mM H{sub 2}O{sub 2} after 24 hr reaction. This catalyzed degradation of organopollutants could be used as a novel technology for hazardous waste remediation.

Kang, G.; Jung, J.; Park, K. [Hankuk Univ. of Foreign Studies, Seoul (Korea, Democratic People`s Republic of); Stevens, D.K. [Utah State Univ., Logan, UT (United States)

1995-12-31

96

PERSPECTIVE Is the simplest chemical reaction really  

E-print Network

Aoizd a Department of Chemistry, Stanford University, Stanford, CA 94305-5080; b Max Born Institute The reaction in which a hydrogen atom collides with a hydrogen molecule to form a new hydrogen molecule plus (Fig. 2) in which the angle between the forming Ha­Hb bond and the breaking Hb­Hc bond is held fixed

Zare, Richard N.

97

Laboratory studies of sticking coefficients and heterogeneous reactions important in the stratosphere  

NASA Technical Reports Server (NTRS)

The discovery of ozone depletion during spring in the Antarctic stratosphere has received wide spread attention. Both meteorological and chemical mechanisms have been used in attempts to explain this observation. The chemical theory focused on the chlorofluoromethanes released into the atmosphere. However, gas-phase, homogeneous reactions alone in the model can not adequately explain such a depletion. Heterogeneous reactions on ice surfaces could be important in the Antarctic stratosphere. These reactions are thought to convert ClONO2 and N2O5 into HNO3 in the solid phase while Cl2, HOCl, and ClNO2 are released into the stratosphere as gas-phase products. The photolysis of Cl2, HOCl, and ClNO2, then produces active chlorine which subsequently removes ozone through several catalytic cycles, including the Cl2O2 mechanism. The polar stratospheric clouds are thought to consist of mixtures of water ice, nitric acid, and sulfuric acid. Condensation of HCl onto the PSC's could provide active surfaces for heterogeneous reactions.

Leu, Ming-Taun

1988-01-01

98

Results of the 2010 Survey on Teaching Chemical Reaction Engineering  

ERIC Educational Resources Information Center

A survey of faculty teaching the chemical reaction engineering course or sequence during the 2009-2010 academic year at chemical engineering programs in the United States and Canada reveals change in terms of content, timing, and approaches to teaching. The report consists of two parts: first, a statistical and demographic characterization of the…

Silverstein, David L.; Vigeant, Margot A. S.

2012-01-01

99

Thermochemistry of silicon carbide growth by chemical transport reactions  

Microsoft Academic Search

Chemical Vapour Transport is a well known process widely used for the growth of monocrystals. This paper is a thermodynamic overview of different heterogeneous chemical systems, promising for the growth of silicon carbide by means of chemical transport reactions. The systems are Si-C-Y where Y is oxygen or a chalcogen (S, Se) and Si-C-H-X where X is an halogen (Cl,

D. Chaussende; G. Ferro; Y. Monteil; C. Brylinski; J. Bouix

2001-01-01

100

LIGAND: Database of Chemical Compounds and Reactions in Biological Pathways  

NSDL National Science Digital Library

The Institute for Chemical Research at Kyoto University provides this frequently updated and well-documented database of enzyme reactions. With more than 9,300 entries, the LIGAND Chemical Database includes over 3,700 entries for enzymes (the Enzyme Reaction Database) and 5,600 entries for compounds (Chemical Compound Database). The database is searchable by keyword using DBGET (which supports numerous other databases and gene catalogs as well) and is accompanied by clear instructions. The LIGAND database, updated weekly, may be downloaded via anonymous FTP.

101

Single-molecule chemical reaction reveals molecular reaction kinetics and dynamics.  

PubMed

Understanding the microscopic elementary process of chemical reactions, especially in condensed phase, is highly desirable for improvement of efficiencies in industrial chemical processes. Here we show an approach to gaining new insights into elementary reactions in condensed phase by combining quantum chemical calculations with a single-molecule analysis. Elementary chemical reactions in liquid-phase, revealed from quantum chemical calculations, are studied by tracking the fluorescence of single dye molecules undergoing a reversible redox process. Statistical analyses of single-molecule trajectories reveal molecular reaction kinetics and dynamics of elementary reactions. The reactivity dynamic fluctuations of single molecules are evidenced and probably arise from either or both of the low-frequency approach of the molecule to the internal surface of the SiO2 nanosphere or the molecule diffusion-induced memory effect. This new approach could be applied to other chemical reactions in liquid phase to gain more insight into their molecular reaction kinetics and the dynamics of elementary steps. PMID:24963600

Zhang, Yuwei; Song, Ping; Fu, Qiang; Ruan, Mingbo; Xu, Weilin

2014-01-01

102

[Research on chemical reactions during ginseng processing].  

PubMed

As a kind of commonly used traditional Chinese medicine, ginseng has a high reputation at home and abroad. The research of ginseng has been expanded to medicine, pharmacy, biology, food science and other fields, with great achievements in recent years. Ginseng contains ginsenosides, volatile oil, carbohydrates, amino acids, polypeptides, inorganic elements and othser chemical constituents. Each component has extensive physiological activity, and is the base of ginseng's effect. After processing, the complicated changes are taken place in the constituents of ginseng, and some new substances produced. This paper aims to review the studies on chemical constituents and their mechanisms during ginseng processing, and the ideas, methods and the direction of the development of traditional Chinese medicine processing in the future. PMID:25612424

Zhang, Miao; Qin, Kun-Ming; Li, Wei-Dong; Yin, Fang-Zhou; Cai, Hao; Cai, Bao-Chang

2014-10-01

103

Automatic NMR-based identification of chemical reaction types in mixtures of co-occurring reactions.  

PubMed

The combination of chemoinformatics approaches with NMR techniques and the increasing availability of data allow the resolution of problems far beyond the original application of NMR in structure elucidation/verification. The diversity of applications can range from process monitoring, metabolic profiling, authentication of products, to quality control. An application related to the automatic analysis of complex mixtures concerns mixtures of chemical reactions. We encoded mixtures of chemical reactions with the difference between the (1)H NMR spectra of the products and the reactants. All the signals arising from all the reactants of the co-occurring reactions were taken together (a simulated spectrum of the mixture of reactants) and the same was done for products. The difference spectrum is taken as the representation of the mixture of chemical reactions. A data set of 181 chemical reactions was used, each reaction manually assigned to one of 6 types. From this dataset, we simulated mixtures where two reactions of different types would occur simultaneously. Automatic learning methods were trained to classify the reactions occurring in a mixture from the (1)H NMR-based descriptor of the mixture. Unsupervised learning methods (self-organizing maps) produced a reasonable clustering of the mixtures by reaction type, and allowed the correct classification of 80% and 63% of the mixtures in two independent test sets of different similarity to the training set. With random forests (RF), the percentage of correct classifications was increased to 99% and 80% for the same test sets. The RF probability associated to the predictions yielded a robust indication of their reliability. This study demonstrates the possibility of applying machine learning methods to automatically identify types of co-occurring chemical reactions from NMR data. Using no explicit structural information about the reactions participants, reaction elucidation is performed without structure elucidation of the molecules in the mixtures. PMID:24551112

Latino, Diogo A R S; Aires-de-Sousa, João

2014-01-01

104

Laser cutting with chemical reaction assist  

DOEpatents

A method is described for cutting with a laser beam where an oxygen-hydrocarbon reaction is used to provide auxiliary energy to a metal workpiece to supplement the energy supplied by the laser. Oxygen is supplied to the laser focus point on the workpiece by a nozzle through which the laser beam also passes. A liquid hydrocarbon is supplied by coating the workpiece along the cutting path with the hydrocarbon prior to laser irradiation or by spraying a stream of hydrocarbon through a nozzle aimed at a point on the cutting path which is just ahead of the focus point during irradiation. 1 figure.

Gettemy, D.J.

1992-11-17

105

An Efficient Chemical Reaction Optimization Algorithm for Multiobjective Optimization.  

PubMed

Recently, a new metaheuristic called chemical reaction optimization was proposed. This search algorithm, inspired by chemical reactions launched during collisions, inherits several features from other metaheuristics such as simulated annealing and particle swarm optimization. This fact has made it, nowadays, one of the most powerful search algorithms in solving mono-objective optimization problems. In this paper, we propose a multiobjective variant of chemical reaction optimization, called nondominated sorting chemical reaction optimization, in an attempt to exploit chemical reaction optimization features in tackling problems involving multiple conflicting criteria. Since our approach is based on nondominated sorting, one of the main contributions of this paper is the proposal of a new quasi-linear average time complexity quick nondominated sorting algorithm; therebymaking our multiobjective algorithm efficient from a computational cost viewpoint. The experimental comparisons against several other multiobjective algorithms on a variety of benchmark problems involving various difficulties show the effectiveness and the efficiency of this multiobjective version in providing a wellconverged and well-diversified approximation of the Pareto front. PMID:25373137

Bechikh, Slim; Chaabani, Abir; Said, Lamjed Ben

2014-10-30

106

Process for the preparation of hydrogen. [series of chemical reactions based on cadmium with water reaction  

Microsoft Academic Search

Hydrogen is produced from water by the addition of heat to a series of chemical reactions which comprise the reaction of cadmium with water, and the subsequent recovery of the cadmium for re-use. The equipment used to produce the hydrogen requires only the input of water and heat to produce an output of hydrogen and oxygen gas.

duPont

1977-01-01

107

Detailed Chemical Kinetic Reaction Mechanisms for Incineration of Organophosphorus and Fluoro-Organophosphorus Compounds  

SciTech Connect

A detailed chemical kinetic reaction mechanism is developed to describe incineration of the chemical warfare nerve agent sarin (GB), based on commonly used principles of bond additivity and hierarchical reaction mechanisms. The mechanism is based on previous kinetic models of organophosphorus compounds such as TMP, DMMP and DIMP that are often used as surrogates to predict incineration of GB. Kinetic models of the three surrogates and GB are then used to predict their consumption in a perfectly stirred reactor fueled by natural gas to simulate incineration of these chemicals. Computed results indicate that DIMP is the only one of these surrogates that adequately describes combustion of GB under comparable conditions. The kinetic pathways responsible for these differences in reactivity are identified and discussed. The most important reaction in GB and DIMP that makes them more reactive than TMP or DMMP is found to be a six-center molecular elimination reaction producing propene.

Glaude, P A; Melius, C; Pitz, W J; Westbrook, C K

2001-12-13

108

Adaptively biased sequential importance sampling for rare events in reaction networks with comparison to exact solutions from finite buffer  

E-print Network

sequential importance sampling (ABSIS) method for efficient probability estimation. By adopting a look. The ABSIS al- gorithm can automatically detect barrier-crossing regions, and can adjust bias adaptively of the reactions and the complexity of the network. We have applied the ABSIS method to four bio- chemical networks

Dai, Yang

109

Primary Chemical Reactions Induced by Radioactive Nuclear Transformations  

SciTech Connect

A series of chemical reactions is suggested to describe primary chemical transformations induced by Auger electrons from radioactive nuclear decay in glassy and crystalline frozen aqueous media. The mechanism is based on Moessbauer emission spectroscopy data supplemented by data on reactions in the tracks of fast positrons and electrons in an aqueous medium. It is shown that variation of temperature, the degree of crystallinity, the concentration of electron acceptors, etc., results in correlated changes in the yields of the final reaction products--Fe{sup 2+}, Fe{sup 3+} or Sn{sup 2+}, Sn{sup 4+} ions, positronium atoms, and molecular radiolytic hydrogen. These correlations indicate the similarity of chemical processes in the nanometer vicinity of decayed {sup 57}Co and {sup 119m}Sn nuclei and in the tracks of fast positrons and electrons. This similarity is caused by the same behavior of secondary intratrack electrons produced due to ionization losses of fast positrons, electrons, and Auger electrons.

Byakov, V.M.; Stepanov, S.V. [Institute of Theoretical and Experimental Physics, Bol'shaya Cheremushkinskaya ul. 25, Moscow, 117259 (Russian Federation); Kulikov, L.A.; Perfil'ev, Yu.D. [Moscow State University, Vorob'evy gory, Moscow, 119899 (Russian Federation)

2005-06-01

110

Kramers problem for nonequilibrium current-induced chemical reactions  

NASA Astrophysics Data System (ADS)

We discuss the use of tunneling electron current to control and catalyze chemical reactions. Assuming the separation of time scales for electronic and nuclear dynamics we employ Langevin equation for a reaction coordinate. The Langevin equation contains nonconservative current-induced forces and gives nonequilibrium, effective potential energy surface for current-carrying molecular systems. The current-induced forces are computed via Keldysh nonequilibrium Green's functions. Once a nonequilibrium, current-depended potential energy surface is defined, the chemical reaction is modeled as an escape of a Brownian particle from the potential well. We demonstrate that the barrier between the reactant and the product states can be controlled by the bias voltage. When the molecule is asymmetrically coupled to the electrodes, the reaction can be catalyzed or stopped depending on the polarity of the tunneling current.

Dzhioev, Alan A.; Kosov, D. S.

2011-08-01

111

Method and apparatus for controlling gas evolution from chemical reactions  

DOEpatents

The present invention is directed toward monitoring a thermally driven gas evolving chemical reaction with an acoustic apparatus. Signals from the acoustic apparatus are used to control a heater to prevent a run-away condition. A digestion module in combination with a robotic arm further automate physical handling of sample material reaction vessels. The invention is especially useful for carrying out sample procedures defined in EPA Methods SW-846.

Skorpik, James R. (Kennewick, WA); Dodson, Michael G. (Richland, WA)

1999-01-01

112

Method and apparatus for controlling gas evolution from chemical reactions  

DOEpatents

The present invention is directed toward monitoring a thermally driven gas evolving chemical reaction with an acoustic apparatus. Signals from the acoustic apparatus are used to control a heater to prevent a run-away condition. A digestion module in combination with a robotic arm further automate physical handling of sample material reaction vessels. The invention is especially useful for carrying out sample procedures defined in EPA Methods SW-846. 8 figs.

Skorpik, J.R.; Dodson, M.G.

1999-05-25

113

Asymmetric chemical reactions by polarized quantum beams  

NASA Astrophysics Data System (ADS)

One of the most attractive hypothesis for the origin of homochirality in terrestrial bio-organic compounds (L-amino acid and D-sugar dominant) is nominated as "Cosmic Scenario"; a chiral impulse from asymmetric excitation sources in space triggered asymmetric reactions on the surfaces of such space materials as meteorites or interstellar dusts prior to the existence of terrestrial life. 1) Effective asymmetric excitation sources in space are proposed as polarized quantum beams, such as circularly polarized light and spin polarized electrons. Circularly polarized light is emitted as synchrotron radiation from tightly captured electrons by intense magnetic field around neutron stars. In this case, either left-or right-handed polarized light can be observed depending on the direction of observation. On the other hand, spin polarized electrons is emitted as beta-ray in beta decay from radioactive nuclei or neutron fireballs in supernova explosion. 2) The spin of beta-ray electrons is longitudinally polarized due to parity non-conservation in the weak interaction. The helicity (the the projection of the spin onto the direction of kinetic momentum) of beta-ray electrons is universally negative (left-handed). For the purpose of verifying the asymmetric structure emergence in bio-organic compounds by polarized quantum beams, we are now carrying out laboratory simulations using circularly polarized light from synchrotron radiation facility or spin polarized electron beam from beta-ray radiation source. 3,4) The target samples are solid film or aqueous solution of racemic amino acids. 1) K.Kobayashi, K.Kaneko, J.Takahashi, Y.Takano, in Astrobiology: from simple molecules to primitive life; Ed. V.Basiuk; American Scientific Publisher: Valencia, 2008. 2) G.A.Gusev, T.Saito, V.A.Tsarev, A.V.Uryson, Origins Life Evol. Biosphere. 37, 259 (2007). 3) J.Takahashi, H.Shinojima, M.Seyama, Y.Ueno, T.Kaneko, K.Kobayashi, H.Mita, M.Adachi, M.Hosaka, M.Katoh, Int. J. Mol. Sci. 10, 3044 (2009). 4) V.I.Burkov, L.A.Goncharova, G.A.Gusev, H.Hashimoto, F.Kaneko, T.Kaneko, K. Kobayashi, H.Mita, E.V.Moiseenko, T.Ogawa, N.G.Poluhina, T.Saito, S.Shima, J.Takahashi, M.Tanaka, Y.Tao, V.A.Tsarev, J.Xu, H.Yabuta, K.Yagi-Watanabe, H.Yan, G.Zhang, Origins Life Evol. Biosphere, 39 295 (2009).

Takahashi, Jun-Ichi; Kobayashi, Kensei

114

CHARACTERIZATION OF CHEMICALLY MODIFIED HYPERTHERMOPHILIC ENZYMES FOR CHEMICAL SYNTHESES AND BIOREMEDIATION REACTIONS  

EPA Science Inventory

Research developments in the area of biocatalysis in organic solvents are expected to greatly expand the role of bioprocessing in chemical synthesis, fuel processing, and bioremediation technologies. Many biological transformation reactions of interest to DOE site remediation inv...

115

Chemical generation of atomic iodine for chemical oxygen iodine laser. I. Modelling of reaction systems  

NASA Astrophysics Data System (ADS)

The mathematical modelling of reaction systems for chemical generation of atomic iodine is presented. This process is aimed to be applied in the chemical oxygen-iodine laser (COIL), where it can save a substantial part of energy of singlet oxygen and so increase the laser output power. In the suggested method, gaseous reactants for I atoms generation are admixed into the COIL primary gas flow containing singlet oxygen. Two reaction systems were proposed, based on the reaction of hydrogen iodide with chemically generated atomic fluorine or chlorine. It was found that the reaction path via Cl atoms better matches the experimental conditions of COIL with a yield of atomic iodine of up to 67%. As a result of modelling, a suitable reaction system and design of experimental arrangement for the effective production of atomic iodine in laser conditions were found.

Jirásek, Vít.; Špalek, Otomar; Kodymová, Jarmila; ?enský, Miroslav

2001-07-01

116

Chemical pathways in ultracold reactions of SrF molecules  

SciTech Connect

We present a theoretical investigation of the chemical reaction SrF + SrF {yields} products, focusing on reactions at ultralow temperatures. We find that bond swapping SrF + SrF {yields} Sr{sub 2} + F{sub 2} is energetically forbidden at these temperatures. Rather, the only energetically allowed reaction is SrF + SrF {yields} SrF{sub 2} + Sr, and even then only singlet states of the SrF{sub 2} trimer can form. A calculation along a reduced reaction path demonstrates that this abstraction reaction is barrierless and proceeds by one SrF molecule ''handing off'' a fluorine atom to the other molecule.

Meyer, Edmund R.; Bohn, John L. [JILA, NIST, and Department of Physics, University of Colorado, Boulder, Colorado 80309-0440 (United States)

2011-03-15

117

Favorite Demonstration: Demonstrating Indigo Carmine Oxidation-Reduction Reactions--A Choreography for Chemical Reactions  

NSDL National Science Digital Library

The indigo carmine demonstration (Ferguson et al. 1973), also referred to as a traffic-light demonstration (Flinn Scientific 2007a), is an example of a set of oxidation-reduction reactions that occurs within one solution. This type of demonstration can be used to introduce the concept of chemical reaction to undergraduate nonscience majors. Through their observations guided by the instructor, students begin to develop and construct the following concepts: color changes, reaction rates, reversible reactions, energy requirements (endothermic/exothermic), and equilibrium.

Majerich, David M.; Schmuckler, Joseph S.

2008-03-01

118

Program Helps To Determine Chemical-Reaction Mechanisms  

NASA Technical Reports Server (NTRS)

General Chemical Kinetics and Sensitivity Analysis (LSENS) computer code developed for use in solving complex, homogeneous, gas-phase, chemical-kinetics problems. Provides for efficient and accurate chemical-kinetics computations and provides for sensitivity analysis for variety of problems, including problems involving honisothermal conditions. Incorporates mathematical models for static system, steady one-dimensional inviscid flow, reaction behind incident shock wave (with boundary-layer correction), and perfectly stirred reactor. Computations of equilibrium properties performed for following assigned states: enthalpy and pressure, temperature and pressure, internal energy and volume, and temperature and volume. Written in FORTRAN 77 with exception of NAMELIST extensions used for input.

Bittker, D. A.; Radhakrishnan, K.

1995-01-01

119

Chemical Kinetic Data Base for Propellant Combustion. II. Reactions Involving CN, NCO, and HNCO  

Microsoft Academic Search

This paper contains evaluated chemical kinetic data on single step elementary reactions involving small polyatomic molecules which are of importance in propellant combustion. The work consists of the collection and evaluation of mechanistic and rate information and the use of various methods for the extrapolation and estimation of rate data where information does not exist. The conditions covered range from

Wing Tsang

1992-01-01

120

2011 Chemical Reactions at Surfaces Gordon Research Conference  

SciTech Connect

The Gordon Research Conference on Chemical Reactions at Surfaces is dedicated to promoting and advancing the fundamental science of interfacial chemistry and physics by providing surface scientists with the foremost venue for presentation and discussion of research occurring at the frontiers of their fields.

Peter Stair

2011-02-11

121

Molecular Codes in Biological and Chemical Reaction Networks  

PubMed Central

Shannon’s theory of communication has been very successfully applied for the analysis of biological information. However, the theory neglects semantic and pragmatic aspects and thus cannot directly be applied to distinguish between (bio-) chemical systems able to process “meaningful” information from those that do not. Here, we present a formal method to assess a system’s semantic capacity by analyzing a reaction network’s capability to implement molecular codes. We analyzed models of chemical systems (martian atmosphere chemistry and various combustion chemistries), biochemical systems (gene expression, gene translation, and phosphorylation signaling cascades), an artificial chemistry, and random reaction networks. Our study suggests that different chemical systems posses different semantic capacities. No semantic capacity was found in the model of the martian atmosphere chemistry, the studied combustion chemistries, and highly connected random networks, i.e. with these chemistries molecular codes cannot be implemented. High semantic capacity was found in the studied biochemical systems and in random reaction networks where the number of second order reactions is twice the number of species. We conclude that our approach can be applied to evaluate the information processing capabilities of a chemical system and may thus be a useful tool to understand the origin and evolution of meaningful information, e.g. in the context of the origin of life. PMID:23372756

Görlich, Dennis; Dittrich, Peter

2013-01-01

122

WATER AS A REACTION MEDIUM FOR CLEAN CHEMICAL PROCESSES.  

EPA Science Inventory

Green chemistry is a rapid developing new field that provides us a pro-active avenue for the sustainable development of future science and technologies. When designed properly, clean chemical technology can be developed in water as a reaction media. The technologies generated f...

123

Dissipation Scale Fluctuations and Chemical Reaction Rates in Turbulent Flows  

E-print Network

Small separation between reactants, not exceeding $10^{-8}-10^{-7}cm$, is the necessary condition for various chemical reactions. It is shown that random advection and stretching by turbulence leads to formation of scalar-enriched sheets of {\\it strongly fluctuating thickness} $\\eta_{c}$. The molecular-level mixing is achieved by diffusion across these sheets (interfaces) separating the reactants. Since diffusion time scale is $\\tau_{d}\\propto \\eta_{c}^{2}$, the knowledge of probability density $Q(\\eta_{c},Re)$ is crucial for evaluation of chemical reaction rates. In this paper we derive the probability density $Q(\\eta_{c},Re,Sc)$ and predict a transition in the reaction rate behavior from ${\\cal R}\\propto \\sqrt{Re}$ ($Re\\leq 10^{4}$) to the high-Re asymptotics ${\\cal R}\\propto Re^{0}$. The theory leads to an approximate universality of transitional Reynolds number $Re_{tr}\\approx 10^{4}$. It is also shown that if chemical reaction involves short-lived reactants, very strong anomalous fluctuations of the length-scale $\\eta_{c}$ may lead to non-negligibly small reaction rates.

Victor Yakhot

2007-06-29

124

Chemical generation of atomic iodine for chemical oxygen–iodine laser. I. Modelling of reaction systems  

Microsoft Academic Search

The mathematical modelling of reaction systems for chemical generation of atomic iodine is presented. This process is aimed to be applied in the chemical oxygen–iodine laser (COIL), where it can save a substantial part of energy of singlet oxygen and so increase the laser output power. In the suggested method, gaseous reactants for I atoms generation are admixed into the

V??t Jirásek; Otomar Špalek; Jarmila Kodymová; Miroslav ?enský

2001-01-01

125

Theoretical Chemical Dynamics Studies of Elementary Combustion Reactions  

SciTech Connect

The purpose of this research was the development and application of theoretical/computational methods for accurate predictions of the rates of reactions in many-atom systems. The specific aim was to improve computational methods for studying the chemical dynamics of large, complex systems and to obtain a better understanding of the chemical reactions involving large polyatomic molecules and radicals. The focus was on the development an automatic potential energy surface generation algorithm that takes advantage of high-performance computing environments; e.g., software for rate calculations that direct quantum chemistry codes to produce ab initio predictions of reaction rates and related dynamics quantities. Specifically, we developed interpolative moving least-squares (IMLS) methods for accurately fitting ab initio energies to provide global PESs and for use in direct dynamics simulations.

Donald L. Thompson

2006-04-27

126

Shock-induced chemical reactions in organic materials and explosives  

NASA Astrophysics Data System (ADS)

Interrogating chemical reactions behind a shock front is immensely difficult and, as a result, the details of shock-induced chemistry remain poorly understood. Previous research has shown that dimerizations, polymerizations, ring-opening and decomposition reactions can occur under shock compression, depending on molecular structure. Questions regarding the thresholds for incipient reaction, the nature of first and subsequent reaction steps, and the influence of shock input conditions on reaction kinetics remain to be answered. Here, we have applied in-situ electromagnetic gauging at multiple Lagrangian positions to elucidate the evolution of multiple-wave structures associated with shock-induced reactions of several simple functional groups: carbon-carbon double (-C=C-) and triple bonds, and nitriles. The relative order of group reactivity under single shock conditions for these simple molecules is discussed. From measurements of the reactive flow, we have obtained detailed information about the temporal evolution of the waves, and global kinetic rates associated with transformation(s) between partially- and fully-reacted states. Near the reactive thresholds, evolution in particle velocities point to reaction timescales on the order of tens-to-hundreds of nanoseconds. We further compare evidence of reaction from gas gun-driven experiments to recent results using laser-driven shocks. Spectroscopic details will be presented from both types of experiments.

Dattelbaum, Dana; Sheffield, Stephen; McGrane, Shawn; Goodwin, Peter

2012-02-01

127

The Electrochemical Thermodynamics for Chemical Reactions in Dispersed Cells.  

PubMed

There is a large specific surface area in a dispersed cell, so much so that there are some notable differences in thermodynamic quantities for a chemical reaction in the cell because of the strong surface effect. The thermodynamic relations between the electromotive force (emf) and the dispersity of a cell and between each of thermodynamic properties and the dispersivity of the cell are derived, and the effects of degree of dispersion of substances in the cell on the emf and the thermodynamic properties are discussed. The results show that the emf, the equilibrium constant, the entropy for reaction, the heat of reaction, and the enthalpy of reaction vary with the dispersivities of the reactants or/and the products in the cell. And two new concepts, surface emf and dispersion cell, are put forward in this paper. Copyright 1999 Academic Press. PMID:10441416

Yong-Qiang; Chun-Hui; Jin-Chuan

1999-09-01

128

Quantum-chemical approach to serine formation in the interstellar medium: A possible reaction pathway  

NASA Astrophysics Data System (ADS)

Radical-radical and radical-neutral interaction schemes are very important for the formation of comparatively complex molecules in low-temperature chemistry. The formation of amino acids, such as serine, in the interstellar medium is quite difficult. We explored the possibility of serine formation in the interstellar medium through detected interstellar molecules such as CH, CO, and OH by radical-radical and radical-neutral interactions in the gaseous phase using rigorous quantum-chemical calculations. The reaction energies, the low potential barrier and the structures of all the geometries involved in the reaction path show that serine formation is possible in interstellar space via the reaction paths.

Shivani; Singh, Amresh; Gupta, Vineet; Misra, Alka; Tandon, Poonam

2014-03-01

129

Screening in Low Energy Nuclear Reactions of Importance to Astrophysics  

Microsoft Academic Search

Recent experiments in the LUNAR (Laboratory for Underground Nuclear Astrophysics) project have shown anonymously high electron screening may occur during acceleration driven low energy (<400 kV) ion bombardment of solid targets [1]. These effects become particularly important for E\\/ Ue < 100 (here E= ion energy and Ue = electron-screening potential energy). Thus these effects become significant for the understanding

George H. Miley; Heinz Hora; Nie Luo

2004-01-01

130

Shock-induced chemical reactions in simple organic molecules  

NASA Astrophysics Data System (ADS)

Interrogating chemical reactions behind a shock front is immensely difficult and, as a result, the details of shock-induced chemistry remain poorly understood. Previous research has shown that dimerizations, polymerizations, ring-opening and decomposition reactions can occur under shock compression, depending on molecular structure. Questions regarding the thresholds for incipient reaction, the nature of first and subsequent reaction steps, and the influence of shock input conditions on reaction kinetics remain to be answered. Here, we have applied in-situ electromagnetic gauging at multiple Lagrangian positions to elucidate the evolution of multiple-wave structures associated with shock-induced reactions of several simple functional groups: carbon-carbon double (-C=C-) and triple bonds, and nitriles. The relative order of group reactivity under single shock conditions for these simple molecules is discussed. From measurements of the reactive flow, we have obtained detailed information about the temporal evolution of the waves, and global kinetic rates associated with transformation(s) between partially- and fully-reacted states. Near the reactive thresholds, evolution in particle velocities point to reaction timescales on the order of tens-to-hundreds of nanoseconds.

Dattelbaum, Dana M.; Sheffield, S. A.

2012-03-01

131

Photo-induced chemical reaction of trans-resveratrol.  

PubMed

Photo-induced chemical reaction of trans-resveratrol has been studied. UV B, liquid state and sufficient exposure time are essential conditions to the photochemical change of trans-resveratrol. Three principal compounds, cis-resveratrol, 2,4,6-phenanthrenetriol and 2-(4-hydroxyphenyl)-5,6-benzofurandione, were successively generated in the reaction solution of trans-resveratrol (0.25 mM, 100% ethanol) under 100 ?W cm(-2) UV B radiation for 4h. cis-Resveratrol, originated from isomerization of trans-resveratrol, resulted in 2,4,6-phenanthrenetriol through photocyclisation reaction meanwhile loss of 2 H. 2,4,6-Phenanthrenetriol played a role of photosensitizer producing singlet oxygen in the reaction pathway. The singlet oxygen triggered [4+2] cycloaddition reaction of trans-resveratrol, and then resulted in the generation of 2-(4-hydroxyphenyl)-5,6-benzofurandione through photorearrangement and oxidation reaction. The singlet oxygen reaction was closely related to the substrate concentration of trans-resveratrol in solution. PMID:25308653

Zhao, Yue; Shi, Meng; Ye, Jian-Hui; Zheng, Xin-Qiang; Lu, Jian-Liang; Liang, Yue-Rong

2015-03-15

132

Reaction dynamics. Extremely short-lived reaction resonances in Cl + HD (v = 1) ? DCl + H due to chemical bond softening.  

PubMed

The Cl + H2 reaction is an important benchmark system in the study of chemical reaction dynamics that has always appeared to proceed via a direct abstraction mechanism, with no clear signature of reaction resonances. Here we report a high-resolution crossed-molecular beam study on the Cl + HD (v = 1, j = 0) ? DCl + H reaction (where v is the vibrational quantum number and j is the rotational quantum number). Very few forward scattered products were observed. However, two distinctive peaks at collision energies of 2.4 and 4.3 kilocalories per mole for the DCl (v' = 1) product were detected in the backward scattering direction. Detailed quantum dynamics calculations on a highly accurate potential energy surface suggested that these features originate from two very short-lived dynamical resonances trapped in the peculiar H-DCl (v' = 2) vibrational adiabatic potential wells that result from chemical bond softening. We anticipate that dynamical resonances trapped in such wells exist in many reactions involving vibrationally excited molecules. PMID:25554783

Yang, Tiangang; Chen, Jun; Huang, Long; Wang, Tao; Xiao, Chunlei; Sun, Zhigang; Dai, Dongxu; Yang, Xueming; Zhang, Dong H

2015-01-01

133

Electrochemical Reactions During Ru Chemical Mechanical Planarization and Safety Considerations  

NASA Astrophysics Data System (ADS)

We analyzed electrochemical reactions during ruthenium (Ru) chemical mechanical planarization (CMP) using a potentiostat and a quartz crystal microbalance, and considered the potential safety issues. We evaluated the valence number derived from Faraday's law using the dissolution mass change of Ru and total coulomb consumption in the electrochemical reactions for Ru in acidic solution and slurry. The valence numbers of dissolved Ru ions were distributed in the range of 2 to 3.5. As toxic ruthenium tetroxide (RuO4) has a valence number of 8, we were able to conclude that no toxic RuO4 was produced in the actual Ru CMP.

Shima, Shohei; Wada, Yutaka; Tokushige, Katsuhiko; Fukunaga, Akira; Tsujimura, Manabu

2011-05-01

134

Laser studies of chemical reaction and collision processes  

SciTech Connect

This work has concentrated on several interrelated projects in the area of laser photochemistry and photophysics which impinge on a variety of questions in combustion chemistry and general chemical kinetics. Infrared diode laser probes of the quenching of molecules with {open_quotes}chemically significant{close_quotes} amounts of energy in which the energy transferred to the quencher has, for the first time, been separated into its vibrational, rotational, and translational components. Probes of quantum state distributions and velocity profiles for atomic fragments produced in photodissociation reactions have been explored for iodine chloride.

Flynn, G. [Columbia Univ., New York, NY (United States)

1993-12-01

135

Analytical importance of some secondary and threshold reactions induced in nuclear reactors  

Microsoft Academic Search

The feasibility of threshold and secondary reactions as analytical alternatives for some special elements is discussed. Examples of applications, at the author's laboratory for determination of lithium, fluorine, titanium and thallium are presented. The importance of threshold reactions as interferences of capture reactions is also discussed. The pairs of elements where the interference was experimentally evaluated were calcium and titanium,

I. M. Cohen

1991-01-01

136

Implementation of a vibrationally linked chemical reaction model for DSMC  

NASA Technical Reports Server (NTRS)

A new procedure closely linking dissociation and exchange reactions in air to the vibrational levels of the diatomic molecules has been implemented in both one- and two-dimensional versions of Direct Simulation Monte Carlo (DSMC) programs. The previous modeling of chemical reactions with DSMC was based on the continuum reaction rates for the various possible reactions. The new method is more closely related to the actual physics of dissociation and is more appropriate to the particle nature of DSMC. Two cases are presented: the relaxation to equilibrium of undissociated air initially at 10,000 K, and the axisymmetric calculation of shuttle forebody heating during reentry at 92.35 km and 7500 m/s. Although reaction rates are not used in determining the dissociations or exchange reactions, the new method produces rates which agree astonishingly well with the published rates derived from experiment. The results for gas properties and surface properties also agree well with the results produced by earlier DSMC models, equilibrium air calculations, and experiment.

Carlson, A. B.; Bird, Graeme A.

1994-01-01

137

Chemical Characterization and Reactivity of Fuel-Oxidizer Reaction Product  

NASA Technical Reports Server (NTRS)

Fuel-oxidizer reaction product (FORP), the product of incomplete reaction of monomethylhydrazine and nitrogen tetroxide propellants prepared under laboratory conditions and from firings of Shuttle Reaction Control System thrusters, has been characterized by chemical and thermal analysis. The composition of FORP is variable but falls within a limited range of compositions that depend on three factors: the fuel-oxidizer ratio at the time of formation; whether the composition of the post-formation atmosphere is reducing or oxidizing; and the reaction or post-reaction temperature. A typical composition contains methylhydrazinium nitrate, ammonium nitrate, methylammonium nitrate, and trace amounts of hydrazinium nitrate and 1,1-dimethylhydrazinium nitrate. Thermal decomposition reactions of the FORP compositions used in this study were unremarkable. Neither the various compositions of FORP, the pure major components of FORP, nor mixtures of FORP with propellant system corrosion products showed any unusual thermal activity when decomposed under laboratory conditions. Off-limit thruster operations were simulated by rapid mixing of liquid monomethylhydrazine and liquid nitrogen tetroxide in a confined space. These tests demonstrated that monomethylhydrazine, methylhydrazinium nitrate, ammonium nitrate, or Inconel corrosion products can induce a mixture of monomethylhydrazine and nitrogen tetroxide to produce component-damaging energies. Damaging events required FORP or metal salts to be present at the initial mixing of monomethylhydrazine and nitrogen tetroxide.

David, Dennis D.; Dee, Louis A.; Beeson, Harold D.

1997-01-01

138

Separation of the isotopes of boron by chemical exchange reactions  

DOEpatents

The isotopes of boron, .sup.10 B and .sup.11 B, are separated by means of a gas-liquid chemical exchange reaction involving the isotopic equilibrium between gaseous BF.sub.3 and a liquid BF.sub.3 . donor molecular addition complex formed between BF.sub.3 gas and a donor chosen from the group consisting of: nitromethane, acetone, methyl isobutyl ketone, or diisobutyl ketone.

McCandless, Frank P. (Bozeman, MT); Herbst, Ronald S. (Idaho Falls, ID)

1995-01-01

139

Separation of the isotopes of boron by chemical exchange reactions  

DOEpatents

The isotopes of boron, {sup 10}B and {sup 11}B, are separated by means of a gas-liquid chemical exchange reaction involving the isotopic equilibrium between gaseous BF{sub 3} and a liquid BF{sub 3} donor molecular addition complex formed between BF{sub 3} gas and a donor chosen from the group consisting of: nitromethane, acetone, methyl isobutyl ketone, or diisobutyl ketone. 1 Fig.

McCandless, F.P.; Herbst, R.S.

1995-05-30

140

Chemical dynamics in the gas phase: Time-dependent quantum mechanics of chemical reactions  

SciTech Connect

A major goal of this research is to obtain an understanding of the molecular reaction dynamics of three and four atom chemical reactions using numerically accurate quantum dynamics. This work involves: (i) the development and/or improvement of accurate quantum mechanical methods for the calculation and analysis of the properties of chemical reactions (e.g., rate constants and product distributions), and (ii) the determination of accurate dynamical results for selected chemical systems, which allow one to compare directly with experiment, determine the reliability of the underlying potential energy surfaces, and test the validity of approximate theories. This research emphasizes the use of recently developed time-dependent quantum mechanical methods, i.e. wave packet methods.

Gray, S.K. [Argonne National Laboratory, IL (United States)

1993-12-01

141

Laboratory Studies of Homogeneous and Heterogeneous Chemical Processes of Importance in the Upper Atmosphere  

NASA Technical Reports Server (NTRS)

The objective of this study is to conduct measurements of chemical kinetics parameters for reactions of importance in the stratosphere and upper troposphere, and to study the interaction of trace gases such as HCl with ice surfaces in order to elucidate the mechanism of heterogeneous chlorine activation processes, using both a theoretical and an experimental approach. The measurements will be carried out under temperature and pressure conditions covering those applicable to the stratosphere and upper troposphere. The techniques to be employed include turbulent flow - chemical ionization mass spectrometry, and optical ellipsometry. The next section summarizes our research activities during the second year of the project, and the section that follows consists of the statement of work for the third year.

Molina, Mario J.

2001-01-01

142

The nature of chemical reaction-driven tip-streaming  

NASA Astrophysics Data System (ADS)

The discovery of chemical reaction-driven tip-streaming (also known as "an amazing drop") was made about a decade ago during measurements of the dynamic interfacial tension of a water-alkali pendant droplet immersed in oil-linoleic acid. A plausible explanation for this self-sustained ejection of micron sized droplets from the tip of the macroscopic pendant drop was offered at that time and attributed to Marangoni stresses driving the reaction-produced surfactant along the interface. Later, asymptotic theory based on the analysis of a complete fluid dynamical formulation supported this hypothesis. As this discovery promised a way of microdroplet generation without the need for complex microchannel geometries or externally imposed flow or electric fields, we were recently motivated to study the influence of the reagent concentrations and reaction rate on the droplet generation. However, in an attempt to recreate the original experiments, we revealed that the cause for tip-streaming is not what it originally seemed to be. This led to a series of experiments clarifying the role of the Marangoni stresses and the crucial differences from similar phenomena. As the mechanism by which the phenomenon was originally thought to operate was supported by recent theoretical studies, the present work leads to new intriguing questions of existence and conditions under which a chemical reaction alone can drive Marangoni stresses capable of self-sustaining the process of tip-streaming.

Mayer, H. C.; Krechetnikov, R.

2013-05-01

143

Characterization of plastic deformation and chemical reaction in titanium-polytetrafluoroethylene mixture  

NASA Astrophysics Data System (ADS)

The subject of this dissertation is the deformation process of a single metal - polymer system (titanium - polytetrafluoroethylene) and how this process leads to initiation of chemical reaction. Several different kinds of experiments were performed to characterize the behavior of this material to shock and impact. These mechanical conditions induce a rapid plastic deformation of the sample. All of the samples tested had an initial porosity which increased the plastic flow condition. It is currently believed that during the deformation process two important conditions occur: removal of the oxide layer from the metal and decomposition of the polymer. These conditions allow for rapid chemical reaction. The research from this dissertation has provided insight into the complex behavior of plastic deformation and chemical reactions in titanium - polytetrafluoroethylene (PTFE, Teflon). A hydrodynamic computational code was used to model the plastic flow for correlation with the results from the experiments. The results from this work are being used to develop an ignition and growth model for metal/polymer systems. Three sets of experiments were used to examine deformation of the 80% Ti and 20% Teflon materials: drop- weight, gas gun, and split-Hopkinson pressure bar. Recovery studies included post shot analysis of the samples using x-ray diffraction. Lagrangian hydrocode DYNA2D modeling of the drop-weight tests was performed for comparison with experiments. One of the reactions know to occur is Ti + C ? TiC (s) which results in an exothermic release. However, the believed initial reactions occur between Ti and fluorine which produces TixFy gases. The thermochemical code CHEETAH was used to investigate the detonation products and concentrations possible during Ti - Teflon reaction. CHEETAH shows that the Ti - fluorine reactions are thermodynamically favorable. This research represents the most comprehensive to date study of deformation induced chemical reaction in metal/polymers.

Davis, Jeffery Jon

1998-09-01

144

Physio-chemical reactions in recycle aggregate concrete.  

PubMed

Concrete waste constitutes the major proportion of construction waste at about 50% of the total waste generated. An effective way to reduce concrete waste is to reuse it as recycled aggregate (RA) for the production of recycled aggregate concrete (RAC). This paper studies the physio-chemical reactions of cement paste around aggregate for normal aggregate concrete (NAC) and RAC mixed with normal mixing approach (NMA) and two-stage mixing approach (TSMA) by differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). Four kinds of physio-chemical reactions have been recorded from the concrete samples, including the dehydration of C(3)S(2)H(3), iron-substituted ettringite, dehydroxylation of CH and development of C(6)S(3)H at about 90 degrees C, 135 degrees C, 441 degrees C and 570 degrees C, respectively. From the DSC results, it is confirmed that the concrete samples with RA substitution have generated less amount of strength enhancement chemical products when compared to those without RA substitution. However, the results from the TSMA are found improving the RAC quality. The pre-mix procedure of the TSMA can effectively develop some strength enhancing chemical products including, C(3)S(2)H(3), ettringite, CH and C(6)S(3)H, which shows that RAC made from the TSMA can improve the hydration processes. PMID:18718710

Tam, Vivian W Y; Gao, X F; Tam, C M; Ng, K M

2009-04-30

145

Computational Analyses of Complex Flows with Chemical Reactions  

NASA Astrophysics Data System (ADS)

The heat and mass transfer phenomena in micro-scale for the mass transfer phenomena on drug in cylindrical matrix system, the simulation of oxygen/drug diffusion in a three dimensional capillary network, and a reduced chemical kinetic modeling of gas turbine combustion for Jet propellant-10 have been studied numerically. For the numerical analysis of the mass transfer phenomena on drug in cylindrical matrix system, the governing equations are derived from the cylindrical matrix systems, Krogh cylinder model, which modeling system is comprised of a capillary to a surrounding cylinder tissue along with the arterial distance to veins. ADI (Alternative Direction Implicit) scheme and Thomas algorithm are applied to solve the nonlinear partial differential equations (PDEs). This study shows that the important factors which have an effect on the drug penetration depth to the tissue are the mass diffusivity and the consumption of relevant species during the time allowed for diffusion to the brain tissue. Also, a computational fluid dynamics (CFD) model has been developed to simulate the blood flow and oxygen/drug diffusion in a three dimensional capillary network, which are satisfied in the physiological range of a typical capillary. A three dimensional geometry has been constructed to replicate the one studied by Secomb et al. (2000), and the computational framework features a non-Newtonian viscosity model for blood, the oxygen transport model including in oxygen-hemoglobin dissociation and wall flux due to tissue absorption, as well as an ability to study the diffusion of drugs and other materials in the capillary streams. Finally, a chemical kinetic mechanism of JP-10 has been compiled and validated for a wide range of combustion regimes, covering pressures of 1atm to 40atm with temperature ranges of 1,200 K--1,700 K, which is being studied as a possible Jet propellant for the Pulse Detonation Engine (PDE) and other high-speed flight applications such as hypersonic missiles. The comprehensive skeletal mechanism consists of 58 species and 315 reactions including in CPD, Benzene formation process by the theory for polycyclic aromatic hydrocarbons (PAH) and soot formation process on the constant volume combustor, premixed flame characteristics.

Bae, Kang-Sik

146

Significance of vapor phase chemical reactions on CVD rates predicted by chemically frozen and local thermochemical equilibrium boundary layer theories  

NASA Technical Reports Server (NTRS)

This paper investigates the role played by vapor-phase chemical reactions on CVD rates by comparing the results of two extreme theories developed to predict CVD mass transport rates in the absence of interfacial kinetic barrier: one based on chemically frozen boundary layer and the other based on local thermochemical equilibrium. Both theories consider laminar convective-diffusion boundary layers at high Reynolds numbers and include thermal (Soret) diffusion and variable property effects. As an example, Na2SO4 deposition was studied. It was found that gas phase reactions have no important role on Na2SO4 deposition rates and on the predictions of the theories. The implications of the predictions of the two theories to other CVD systems are discussed.

Gokoglu, Suleyman A.

1988-01-01

147

Automated microreactor system for reaction development and online optimization of chemical processes  

E-print Network

Developing the optimal conditions for chemical reactions that are common in fine chemical and pharmaceutics is a difficult and expensive task. Because syntheses in these fields have multiple reaction pathways, a significant ...

McMullen, Jonathan Patrick

2010-01-01

148

Chemical and mechanical feedback during reaction rim growth  

NASA Astrophysics Data System (ADS)

The system MgO-SiO2, including the mineral reaction quadruple periclase-forsterite-enstatite-quartz, has for several years become a favored target for laboratory and thought experiments on reaction rim growth, on the possible grain-scale pressure variability evolving during metamorphic reactions, and on the role of the local reaction volume in guiding kinetic pathways. Both isotope tracer and microstructure analyses indicate that the relative opposite fluxes of MgO and SiO2 components obey the limitations in space dictated by the stoichiometry of the local partial reactions. However, if the component's mobility is high, this implies local competition between mineral growth and the yield strength of the surrounding matrix, thus local pressure variation. Experimentally this is validated by the significant differences in Opx rim thickness, either forming around Ol in Qtz matrix, or around Qtz in Ol matrix, in one and the same experiment. Tantamount observations have been experimentally made in the CaO-SiO2 and CaO-MgO-SiO2 systems. In all these laboratory experiments, the presence of traces of water has been identified as a leading variable controlling the mobility of chemical species. Trace amounts of water follow local pressure gradients and speed up reaction rates where local volume change is negative. New results indicate that at least in coarse grained rocks, total water contents in the 10 ppm range might increase chemical fluxes along grain boundaries by orders of magnitude. The majority of metamorphic rocks in the Earth's crust is dominated by aluminuous silicates and quartz. Reaction rims in aluminosilicate lithologies have been studied in samples of high-pressure felsic granulites from the Bohemian Massif (Variscan belt of Central Europe). They show well developed plagioclase reaction rims around kyanite grains in two microstructural settings. Plagioclase rims around kyanite inclusions within large perthites have a radial thickness of up to 50 ?m, whereas the radial thickness of plagioclase rims around kyanites in the polycrystalline matrix is significantly larger, up to 200 ?m. The difference in the rim thickness for the two microstructural settings is ascribed to the complex interplay of the efficiency of chemical mass transfer and the mechanical response of the surrounding matrix next to the reaction site. Our data based on numerical modelling show that the microstructure may be generated and maintained on the geological time scale as a result of the mechanical feedback induced by the local reactions taking place in restricted space. In general, the observations from experimental and natural systems indicate that assumed equilibria in metamorphic rocks must be generally considered as local equilibria. This includes not only the chemical composition of metamorphic minerals, but also the strength of the surrounding matrix in which they form.

Milke, R.; Tajcmanova, L.

2012-12-01

149

Anaphylactic reactions to low-molecular weight chemicals.  

PubMed

Low-molecular weight chemicals (haptens) include a large group of chemical compounds occurring in work environment, items of everyday use (cleaning products, clothing, footwear, gloves, furniture), jewelry (earrings, bracelets), drugs, especially in cosmetics. They cause type IV hypersensitive reactions. During the induction phase of delayed-type hypersensitivity, haptens form complexes with skin proteins. After internalization through antigen presenting cells, they are bound to MHC class II molecules. Next, they are exposed against specific T-lymphocytes, what triggers activation of Th1 cells mainly. After repeating exposition to that hapten, during effector phase, Th1 induce production of cytokines affecting non-specific inflammatory cells. Usually, it causes contact dermatitis. However, occasionally incidence of immediate generalized reactions after contact with some kinds of haptens is noticed. A question arises, how the hapten does induce symptoms which are typical for anaphylaxis, and what contributes to amplification of this mechanism. It seems that this phenomenon arises from pathomechanism occurring in contact urticaria syndrome in which an anaphylactic reaction may be caused either by contact of sensitized skin with protein antigens, high-molecular weight allergens, or haptens. One of the hypotheses indicates the leading role of basophiles in this process. Their contact with haptens, may cause to release mediators of immediate allergic reaction (histamine, eicosanoids) and to produce cytokines corresponding to Th2 cells profile. Furthermore, Th17 lymphocytes secreting pro-inflammatory interleukin-17 might be engaged into amplifying hypersensitivity into immediate reactions and regulatory T-cells may play role in the process, due to insufficient control of the activity of effector cells. PMID:25661919

Nowak, Daria; Panaszek, Bernard

2015-01-01

150

Mass Spectroscopy of Chemical Reaction of 3d Metal Clusters Involved in Chemical Vapor Deposition Synthesis of Carbon Nanotubes  

E-print Network

, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan The chemical reactions of transition metalMass Spectroscopy of Chemical Reaction of 3d Metal Clusters Involved in Chemical Vapor Deposition clusters in the gas phase have aroused considerable scientific interest and are also of critical scientific

Maruyama, Shigeo

151

Holistic Metrics for Assessment of the Greenness of Chemical Reactions in the Context of Chemical Education  

ERIC Educational Resources Information Center

Two new semiquantitative green chemistry metrics, the green circle and the green matrix, have been developed for quick assessment of the greenness of a chemical reaction or process, even without performing the experiment from a protocol if enough detail is provided in it. The evaluation is based on the 12 principles of green chemistry. The…

Ribeiro, M. Gabriela T. C.; Machado, Adelio A. S. C.

2013-01-01

152

Theory of reversible associative-dissociative diffusion-influenced chemical reaction. II. Bulk reaction  

NASA Astrophysics Data System (ADS)

A many-particle homogeneous reacting system of reactants, where bulk reversible reaction A + B ? C takes place, is considered in the framework of the kinetic theory approach. The various forms of kinetic equations in the thermodynamic limit are obtained, and important relations between kinetic coefficients characterizing the course of bulk and the corresponding geminate reactions are established. Based on the kinetic equations derived, different results available in the literature have been analyzed. Universal long-term kinetic laws of the reaction course are deduced.

Kipriyanov, Alexey A.; Doktorov, Alexander B.

2013-01-01

153

Theory of reversible associative-dissociative diffusion-influenced chemical reaction. I. Geminate reaction  

NASA Astrophysics Data System (ADS)

A many-particle, in the general case, inhomogeneous reacting system of independent pairs of reactants, where geminate reversible reaction A+Brightleftarrows C takes place, is considered in the framework of the kinetic theory approach. The kinetic equations in the thermodynamic limit are obtained, and important relations between kinetic coefficients characterizing the reaction course are established, as well as the relations between the kinetic dependencies under different initial conditions including the relations that extend the familiar literature results to the case of rather realistic model of the reacting system. Universal long-term kinetic laws of the reaction course are determined.

Doktorov, Alexander B.; Kipriyanov, Alexey A.

2011-09-01

154

Tungsten-dependent formaldehyde ferredoxin oxidoreductase: Reaction mechanism from quantum chemical calculations  

E-print Network

redox reactions, while the latter catalyzes a non-redox hydration of acetylene. In Pyrococcus furiosusTungsten-dependent formaldehyde ferredoxin oxidoreductase: Reaction mechanism from quantum chemical April 2011 Keywords: Tungstoenzyme Formaldehyde oxidoreductase Reaction mechanism Density functional

Liao, Rongzhen

155

Computational organic chemistry: bridging theory and experiment in establishing the mechanisms of chemical reactions.  

PubMed

Understanding the mechanisms of chemical reactions, especially catalysis, has been an important and active area of computational organic chemistry, and close collaborations between experimentalists and theorists represent a growing trend. This Perspective provides examples of such productive collaborations. The understanding of various reaction mechanisms and the insight gained from these studies are emphasized. The applications of various experimental techniques in elucidation of reaction details as well as the development of various computational techniques to meet the demand of emerging synthetic methods, e.g., C-H activation, organocatalysis, and single electron transfer, are presented along with some conventional developments of mechanistic aspects. Examples of applications are selected to demonstrate the advantages and limitations of these techniques. Some challenges in the mechanistic studies and predictions of reactions are also analyzed. PMID:25568962

Cheng, Gui-Juan; Zhang, Xinhao; Chung, Lung Wa; Xu, Liping; Wu, Yun-Dong

2015-02-11

156

Thermal energy storage. [by means of chemical reactions  

NASA Technical Reports Server (NTRS)

The principles involved in thermal energy storage by sensible heat, chemical potential energy, and latent heat of fusion are examined for the purpose of evolving selection criteria for material candidates in the low ( 0 C) and high ( 100 C) temperature ranges. The examination identifies some unresolved theoretical considerations and permits a preliminary formulation of an energy storage theory. A number of candidates in the low and high temperature ranges are presented along with a rating of candidates or potential candidates. A few interesting candidates in the 0 to 100 C region are also included. It is concluded that storage by means of reactions whose reversibility can be controlled either by product removal or by catalytic means appear to offer appreciable advantages over storage with reactions whose reversability cannot be controlled. Among such advantages are listed higher heat storage capacities and more favorable options regarding temperatures of collection, storage, and delivery. Among the disadvantages are lower storage efficiencies.

Grodzka, P. G.

1975-01-01

157

Nature of the chemical reaction for furfural modified asphalt  

SciTech Connect

Three of the most serious problems of asphalt pavements today are rutting, cracking, and susceptibility to moisture damage (stripping). Asphalt manufacturers have been mixing asphalts with polymers to produce polymer-modified asphalts with improved rheological properties. However, the costs for these improved polymer-modified asphalts are almost double that of regular asphalts. FHWA researchers have found that asphalt modified by the chemical, furfural (which is prepared by simple elimination reaction of aldopentoses obtained from oat hulls), exhibited better stripping properties and was less temperature susceptible than the virgin asphalt while costing less than polymer-modified asphalts. This paper discusses the possible structure of the furfural-modified asphalt, data for the virgin and furfural-modified asphalts and their Corbett fractions, data from a model reaction between phenol and furfural, and a possible explanation of this structure based on these data.

Memon, G.M.; Chollar, B.H. [FHWA Engineering, Inc., McLean, VA (United States)

1994-12-31

158

Dephosphorylation reactions with deferoxamine, a potential chemical nuclease.  

PubMed

We report a detailed kinetic and mechanistic study of the reaction of a widely used therapeutic agent, deferoxamine (DFO), which contains three nucleophilic hydroxamate groups, with the model phosphate diester bis-2,4-dinitrophenylphosphate BDNPP. We clarify the mechanism by detecting important phosphorylated intermediates in the model reaction and show that the mechanism can be extended to the reaction with DNA. The effectiveness of DFO in cleaving DNA was examined over a range of pH in the absence and presence of a biologically available metal (Zn(2+)). The results inform and complement ongoing studies involving DFO, which can act as a powerful nucleophile toward DNA and other targets susceptible to nucleophilic attack. PMID:22049907

Orth, Elisa S; Medeiros, Michelle; Bortolotto, Tiago; Terenzi, Hernán; Kirby, Anthony J; Nome, Faruk

2011-12-16

159

Effects of exothermic chemical reaction on the photoacoustic effect from particulate suspensions  

Microsoft Academic Search

Irradiation of chemically reactive particulate suspensions by high power, pulsed laser radiation initiates reactions at the sites of the particles so that besides the absorbed optical energy, chemical energy is liberated. In addition to the release of chemical energy, chemical reaction can result in gas production both of which result in enhancement in the amplitude of the photoacoustic effect. Here

Han Jung Park; Binbin Wu; Gerald J. Diebold

2011-01-01

160

Resonant radiofrequency magnetic field effects on a chemical reaction  

NASA Astrophysics Data System (ADS)

Observations of the effect of a radiofrequency magnetic field on the progress of a chemical reaction are reported. It is shown that the fluorescence of an exciplex formed in the photoreaction of anthracene-d 10 and 1,3-dicyanobenzene (DCB) is attenuated when a 30-40 MHz oscillating field is applied. The effect is interpreted in the framework of the radical pair mechanism, in terms of a change in the extent of singlet?triplet interconversion in the {anthracene cation-DCB anion} radical pair when the oscillating field is in resonance with hyperfine splittings in the DCB anion radical.

Woodward, J. R.; Jackson, R. J.; Timmel, C. R.; Hore, P. J.; McLauchlan, K. A.

1997-07-01

161

Method for detecting pollutants. [through chemical reactions and heat treatment  

NASA Technical Reports Server (NTRS)

A method is described for detecting and measuring trace amounts of pollutants of the group consisting of ozone, nitrogen dioxide, and carbon monoxide in a gaseous environment. A sample organic solid material that will undergo a chemical reaction with the test pollutant is exposed to the test environment and thereafter, when heated in the temperature range of 100-200 C., undergoes chemiluminescence that is measured and recorded as a function of concentration of the test pollutant. The chemiluminescence of the solid organic material is specific to the pollutant being tested.

Rogowski, R. S.; Richards, R. R.; Conway, E. J. (inventors)

1976-01-01

162

An Overview of Chemical Processes That Damage Cellular DNA: Spontaneous Hydrolysis, Alkylation, and Reactions with Radicals  

PubMed Central

The sequence of heterocyclic bases on the interior of the DNA double helix constitutes the genetic code that drives the operation of all living organisms. With this said, it is not surprising that chemical modification of cellular DNA can have profound biological consequences. Therefore, the organic chemistry of DNA damage is fundamentally important to diverse fields including medicinal chemistry, toxicology, and biotechnology. This review is designed to provide a brief overview of the common types of chemical reactions that lead to DNA damage under physiological conditions. PMID:19757819

Gates, Kent S.

2009-01-01

163

Chemical reaction rates and non-equilibrium pressure of reacting gas mixtures in the state-to-state approach  

NASA Astrophysics Data System (ADS)

Viscous gas flows with vibrational relaxation and chemical reactions in the state-to-state approach are analyzed. A modified Chapman-Enskog method is used for the determination of chemical reaction and vibrational transition rates and non-equilibrium pressure. Constitutive equations depend on the thermodynamic forces: velocity divergence and chemical reaction/transition affinity. As an application, N2 flow with vibrational relaxation across a shock wave is investigated. Two distinct processes occur behind the shock: for small values of the distance the affinity is large and vibrational relaxation is in its initial stage; for large distances the affinity is small and the chemical reaction is in its final stage. The affinity contributes more to the transition rate than the velocity divergence and the effect of these two contributions are more important for small distances from the shock front. For the non-equilibrium pressure, the term associated with the bulk viscosity increases by a small amount the hydrostatic pressure.

Kustova, Elena V.; Kremer, Gilberto M.

2014-12-01

164

Abiotic reduction reactions of anthropogenic organic chemicals in anaerobic systems: A critical review  

NASA Astrophysics Data System (ADS)

This review is predicated upon the need for a detailed process-level understanding of factors influencing the reduction of anthropogenic organic chemicals in natural aquatic systems. In particular, abiotic reductions of anthropogenic organic chemicals are reviewed. The most important reductive reaction is alkyl dehalogenation (replacement of chloride with hydrogen) which occurs in organisms, sediments, sewage sludge, and reduced iron porphyrin model systems. An abiotic mechanism involving a free radical intermediate has been proposed. The abstraction of vicinal dihalides (also termed dehalogenation) is another reduction that may have an abiotic component in natural systems. Reductive dehalogenation of aryl halides has recently been reported and further study of this reaction is needed. Several other degradation reactions of organohalides that occur in anaerobic environments are mentioned, the most important of which is dehydrohalogenation. The reduction of nitro groups to amines has also been thoroughly studied. The reactions can occur abiotically, and are affected by the redox conditions of the experimental system. However, a relationship between nitro-reduction rate and measured redox potential has not been clearly established. Reductive dealkylation of the N- and O-heteroatom of hydrocarbon pollutants has been observed but not investigated in detail. Azo compounds can be reduced to their hydrazo derivatives and a thorough study of this reaction indicates that it can be caused by extracellular electron transfer agents. Quinone-hydroquinone couples are important reactive groups in humic materials and similar structures in resazurin and indigo carmine make them useful as models for environmental redox conditions. The interconversion of sulfones, sulfoxides, and sulfides is a redox process and is implicated in the degradation of several pesticides though the reactions need more study. Two reductive heterocyclic cleavage reactions are also mentioned. Finally, several difficulties (both semantic and experimental) that recur in the studies reviewed are discussed. The subtle effects of various sterilization techniques on extracellular biochemicals and complex chemical reducing agents in sediment have stifled attempts to separate abiotic from biological degradation reactions. The characterization of redox conditions in a natural system is still problematic since measured redox potential is not adequate. Suggestions for future research toward a process-level understanding of abiotic chemical reductions are made.

Macalady, Donald L.; Tratnyek, Paul G.; Grundl, Timothy J.

1986-02-01

165

Coupling of hydrologic transport and chemical reactions in a stream affected by acid mine drainage  

USGS Publications Warehouse

Experiments in St. Kevin Gulch, an acid mine drainage stream, examined the coupling of hydrologic transport to chemical reactions affecting metal concentrations. Injection of LiCl as a conservative tracer was used to determine discharge and residence time along a 1497-m reach. Transport of metals downstream from inflows of acidic, metal-rich water was evaluated based on synoptic samples of metal concentrations and the hydrologic characteristics of the stream. Transport of SO4 and Mn was generally conservative, but in the subreaches most affected by acidic inflows, transport was reactive. Both 0.1-??m filtered and particulate Fe were reactive over most of the stream reach. Filtered Al partitioned to the particulate phase in response to high instream concentrations. Simulations that accounted for the removal of SO4, Mn, Fe, and Al with first-order reactions reproduced the steady-state profiles. The calculated rate constants for net removal used in the simulations embody several processes that occur on a stream-reach scale. The comparison between rates of hydrologie transport and chemical reactions indicates that reactions are only important over short distances in the stream near the acidic inflows, where reactions occur on a comparable time scale with hydrologic transport and thus affect metal concentrations.

Kimball, B.A.; Broshears, R.E.; Bencala, K.E.; McKnight, D.M.

1994-01-01

166

MODEL OF CHEMICAL REACTION EQUILIBRIUM OF SULFURIC ACID SALTS OF TRIOCTYLAMINE  

Microsoft Academic Search

The chemical reaction of trioctylamine (TOA) and sulfuric acid in organic solvent\\/aqueous solution was carried out. TOA salt products of various kinds were obtained based on different conditions of operation and organic solvents. An equilibrium model, based on the chemical reaction of sulfuric acid and trioctylamine, is proposed. The equilibrium constants of various reactions of trioctylamine and sulfuric acid were

MAW-LING WANG; KWAN-HUA HU

1993-01-01

167

On persistence of chemical reaction networks with time-dependent kinetics and no global conservation laws  

E-print Network

On persistence of chemical reaction networks with time-dependent kinetics and no global work. The new results allow the consideration of reaction rates which are time-varying, thus for persistence of chemical reaction networks are proposed, which extend those obtained by the authors in previous

Sontag, Eduardo

168

Mathematically Reduced Chemical Reaction Mechanism Using Neural Networks  

SciTech Connect

This is the final technical report for the project titled 'Mathematically Reduced Chemical Reaction Mechanism Using Neural Networks'. The aim of the project was to develop an efficient chemistry model for combustion simulations. The reduced chemistry model was developed mathematically without the need of having extensive knowledge of the chemistry involved. To aid in the development of the model, Neural Networks (NN) was used via a new network topology known as Non-linear Principal Components Analysis (NPCA). A commonly used Multilayer Perceptron Neural Network (MLP-NN) was modified to implement NPCA-NN. The training rate of NPCA-NN was improved with the GEneralized Regression Neural Network (GRNN) based on kernel smoothing techniques. Kernel smoothing provides a simple way of finding structure in data set without the imposition of a parametric model. The trajectory data of the reaction mechanism was generated based on the optimization techniques of genetic algorithm (GA). The NPCA-NN algorithm was then used for the reduction of Dimethyl Ether (DME) mechanism. DME is a recently discovered fuel made from natural gas, (and other feedstock such as coal, biomass, and urban wastes) which can be used in compression ignition engines as a substitute for diesel. An in-house two-dimensional Computational Fluid Dynamics (CFD) code was developed based on Meshfree technique and time marching solution algorithm. The project also provided valuable research experience to two graduate students.

Ziaul Huque

2007-08-31

169

Measurements and analysis of alpha-induced reactions of importance for nuclear astrophysics  

NASA Astrophysics Data System (ADS)

Reactions during stellar helium burning are of primary importance for understanding nucleosynthesis. A detailed understanding of the critical reaction chain 4He(2alpha, gamma)12C( alpha, gamma)16O(alpha, gamma) 20Ne is necessary both because it is the primary energy source and because it determines the ratio of 12C to 16O produced, which in turn significantly effects subsequent nucleosynthesis. Also during Helium burning, the reactions 22Ne(alpha, n)25Mg and 22Ne(alpha, gamma )26Mg are crucial in determining the amount of neutrons available for the astrophysical s-process. This thesis presents new experimental results concerning the 16O(alpha, gamma) 20Ne, 22Ne(alpha, n)25Mg, and 22Ne(alpha, gamma)26Mg reaction rates. These results are then applied to the calculation of the associated stellar reaction rates in order to achieve better accuracy.

de Messieres, Genevieve Escande

2011-11-01

170

Enzyme catalysis Enzyme catalysis is the catalysis of chemical reactions by  

E-print Network

Enzyme catalysis Enzyme catalysis is the catalysis of chemical reactions by specialized proteins known as enzymes. Catalysis of biochemical reactions in the cell is vital due to the very low reaction rates of the uncatalysed reactions. The mechanism of enzyme catalysis is similar in principle to other

Cavanagh, John

171

Impact of fluid deformation on mixing-induced chemical reactions in heterogeneous flows  

NASA Astrophysics Data System (ADS)

Fast chemical reactions in geophysical flows are controlled by fluid mixing, which perturbs local chemical equilibria and thus triggers chemical reactions. Spatial fluctuations in the flow velocity lead to deformation of material fluid elements, which form the support volumes of transported chemical species. We develop an approach based on a lamellar representation of fluid mixing that provides a direct link between fluid deformation, the distribution of concentration gradients, and the upscaled reaction rates for fast reversible reactions. The temporal evolution of effective reaction rates is determined by the flow topology and the distribution of local velocity gradients. This leads to a significant increase of the reaction efficiency, which turns out to be orders of magnitude larger than in homogeneous flow. This approach allows for the systematic evaluation of the temporal evolution of equilibrium reaction rates and establishes a direct link between the reaction efficiency and the spatial characteristics of the underlying flow field as quantified by the deformation of material fluid elements.

Borgne, Tanguy Le; Ginn, Timothy R.; Dentz, Marco

2014-11-01

172

SENSITIVITY OF CHEMICAL REACTION NETWORKS: A STRUCTURALAPPROACH. 1. EXAMPLES AND THE CARBON METABOLIC NETWORK  

E-print Network

-1- SENSITIVITY OF CHEMICAL REACTION NETWORKS: A STRUCTURALAPPROACH. 1. EXAMPLES AND THE CARBON for sensitivity Corresponding Author: Atsushi Mochizuki Address: Theoretical Biology Laboratory, RIKEN, Wako 351 examines their "sensitivity": each enzyme mediating a reaction in the system is increased

Fiedler, Bernold

173

Using a Natural Analogue to Investigate Chemical Reactions Associated with Carbon Dioxide Sequestration  

NASA Astrophysics Data System (ADS)

Capture and storage of carbon dioxide in deep underground geologic formations (geologic carbon sequestration) is currently the most advanced technology for reducing or mitigating anthropogenic carbon dioxide emissions. There are a number of scientific challenges associated with injection and storage of large amounts of CO2 in geologic formations. Understanding the chemical reactions that can occur among reservoir rocks, aqueous fluids, and supercritical carbon dioxide ± other gasses is one of these challenges. Natural analogues to CO2 sequestration are systems where carbon dioxide has been stored over geologic time scales. By studying these analogues we can determine important chemical reactions between the host rock and stored gases. The Moxa Arch is a structural feature located in the southern end of the greater Green River Basin, Wyoming. Carbon dioxide and methane were emplaced in Paleozoic rocks, including the 1000 feet thick Mississippian age Madison Limestone, of the Moxa Arch through natural processes. Concentrations of carbon dioxide in the emplaced gas in these formations vary in the region of the Moxa Arch from 70-95% and are as low as ~ 15% in gas producing areas outside of the Moxa Arch. Methane, hydrogen sulfide and helium comprise the balance of the gas compositons. Geochemical reaction path and reactive transport models based upon the mineralogy of 12 core samples collected from three wells completed in the Madison Limestone near the Moxa Arch will be presented. These models help identify potential geochemical reactions between reservoir minerals and stored gasses.

Navarre-Sitchler, A.; Kaszuba, J.; Thyne, G.

2008-12-01

174

Experimental results of exothermic reaction with concentration gradient catalyst in a solar chemical heat pump  

Microsoft Academic Search

A solar chemical heat pump can upgrade low-temperature solar heat of about 80°C to about 150-200°C by using the reversible chemical reactions of 2-propanol\\/acetone\\/hydrogen, which are composed of endothermic and exothermic reactions. In the exothermic process of the above reaction, a temperature peak occurs near the inlet of the reaction zone in the case of uniform catalyst arrangement. Such a

T. Takashima; T. Doi; Y. Ando; T. Tanaka; R. Miyahara; J. Kamoshida

1997-01-01

175

Direct Monte Carlo simulation of chemical reaction systems: Internal energy transfer and an energy-dependent unimolecular reaction  

E-print Network

Direct Monte Carlo simulation of chemical reaction systems: Internal energy transfer and an energy a direct Monte Carlo simulation of an energy-dependent t&molecular reaction system of the type A+ B can be treated by Monte Carlo simulations. One of the most useful methods is Bird's direct simulation

Anderson, James B.

176

Detection of a wide range of medically important fungi by the polymerase chain reaction  

Microsoft Academic Search

Summary. A polymerase chain reaction (PCR) method was developed that was capable of detecting a wide range of medically important fungi from clinical specimens. The primer pair was designed in conserved sequences of 1 8s-ribosomal RNA genes shared by most fungi. The lower limit of detection of this PCR technique was 1 pg of Cundidu ulbicans genomic DNA by ethidium

K. Makimura; SOMAY Y. MURAYAMA; H. Yamaguchi

1994-01-01

177

Application of magnetic microfluidic chip to chemical and electrochemical reactions  

NASA Astrophysics Data System (ADS)

A new type of the microfluidic chip is proposed, which is composed of a network of magnetic channels instead of solid channels. The magnetic channels are formed by the heterogeneous magnetic field distribution (called magnetic walls or magnetic barriers) around a ferromagnetic track imbedded on a chip surface. The channel is surrounded not by solid walls, but by a liquid-liquid interface with a diamagnetic or a paramagnetic solution (called an environmental solution) supported by the magnetic wall. After injecting a solution (called a test solution) with magnetism different from the environmental solution into the channel, the test solution smoothly proceeds into the channel in a frictionless mode. In the static state, the test solution takes a tube-like shape owing to the conventional interfacial tension and the magnetic pressure. The liquid-liquid interface also behaves like a self-repairable, elastic membrane, so that the test solutions, even if mixed with bubbles and solid particles, can smoothly flow without choking. Mass and heat easily transfer through the magnetic wall, so that this system can be applied to effective reactors for various chemical and electrochemical reactions. Figs 10, Refs 27.

Aogaki, R.; Ito, E.; Ogata, M.

2006-12-01

178

Mathematically Reduced Chemical Reaction Mechanism Using Neural Networks  

SciTech Connect

This is an annual technical report for the work done over the last year (period ending 9/30/2004) on the project titled ''Mathematically Reduced Chemical Reaction Mechanism Using Neural Networks''. The aim of the project is to develop an efficient chemistry model for combustion simulations. The reduced chemistry model will be developed mathematically without the need of having extensive knowledge of the chemistry involved. To aid in the development of the model, Neural Networks (NN) will be used via a new network topology know as Non-linear Principal Components Analysis (NPCA). We report on the development of a procedure to speed up the training of NPCA. The developed procedure is based on the non-parametric statistical technique of kernel smoothing. When this smoothing technique is implemented as a Neural Network, It is know as Generalized Regression Neural Network (GRNN). We present results of implementing GRNN on a test problem. In addition, we present results of an in house developed 2-D CFD code that will be used through out the project period.

Nelson Butuk

2004-12-01

179

Chemical reactions between Venus' surface and atmosphere - An update. (Invited)  

NASA Astrophysics Data System (ADS)

The surface of Venus, at ~740K, is hot enough to allow relatively rapid chemical reactions between it and the atmosphere, i.e. weathering. Venus chemical weathering has been explored in detail [1], to the limits of available data. New data from Venus Express (VEx) and new ideas from exoplanets have sparked a modest renewal of interest in Venus weathering. Venus' surface cannot be observed in visible light, but there are several NIR ';windows' through its atmosphere that allow surface imaging. The VIRTIS spectrometer on VEx viewed the surface through one window [2]; emissivity variations among lava flows on Imdr and Themis Regios have been explained as varying degrees of weathering, and thus age [3]. The VMC camera on VEx also provides images through a NIR window, which suggest variable degrees of weathering on some basaltic plains [4]. Indirect evidence for weathering may come from varying SO2 abundance at Venus' cloud tops; repeated rapid increases and gradual declines may represent volcanic eruptions followed by weathering to form sulfate minerals [5]. Continued geochemical modeling relevant to Venus weathering is motivated by expolanet studies [6]. Models have been extended to hypothetical exo-Venuses of different temperatures and surface compositions [7]. The idea that Venus' atmosphere composition can be buffered by reaction with its surface was explored in detail, and the derived constraint extended to other types of planets [8]. Several laboratories are investigating Venus weathering, motivated in part by the hope that they can provide real constraints on timescales of Venus volcanism [3]. Aveline et al. [9] are extending early studies [10] by reacting rocks and minerals with concentrated SO2 (to accelerate reaction rates to allow detectability of products). Kohler et al. [11] are investigating the stability of metals and chalcogenides as possible causes of the low-emissivity surfaces at high elevations. Berger and Aigouy [12] studied rock alteration on a hypothetical early Venus with a water-rich atmosphere. Martin et al. [13] investigated the fate of weathered rock when heated (by igneous or impact events). Our understanding of Venus' geological history is stymied by a lack of data - spacecraft observations of and/or at its surface. VMC on VEx may continue to provide new data on surface emissivity, but their interpretation is inherently ambiguous. Laboratory experiments seem the most promising approach - attempting to quantify rates of weathering and thus volcanism [3], and (with luck) framing significant problems that can be directly answered by spacecraft observations. [1] Fegley B.Jr. et al. (1997) In Venus II. U. Ariz. Press. p. 591. [2] Helbert J. et al. (2008) GRL 35, L11201. [3] Smrekar S.E et al. (2010) Science 328, 605-608. [4] Basilevsky A.T. et al. (2012) Icarus 217, 434-450. [5] Marcq E. et al. (2013) Nature Geoscience 6, 25-28. [6] Kane S.R. et al. (2013) Astrophysical J. 770, L20. [7] Schaefer L. & Fegley B.Jr. (2011) Astrophysical J. 729, 6. [8] Treiman A.H. & Bullock M.A. (2012) Icarus 217, 534-541. [9] Aveline D.C. et al. (2011) Lunar Planet. Sci. Conf. 42, Abstr. #2165. [10] Fegley B.Jr. & Prinn R.G. (1989) Nature 337, 55-58. [11] Kohler E. et al. (2012) Lunar Planet. Sci. Conf. 43, Abstr. #2749. [12] Berger G. & Aigouy T. (2011) Lunar Planet. Sci. Conf. 42, Abstr. #1660. [13] Martin A.M. et al. (2012) Earth Planet. Sci. Lett. 331-332, 291-304.

Treiman, A. H.

2013-12-01

180

Studies in photochemical smog chemistry. 1. Atmospheric chemistry of toulene. 2. Analysis of chemical reaction mechanisms for photochemical smog  

SciTech Connect

This study focuses on two related topics in the gas phase organic chemistry of importance in urban air pollution. An experimental effort aimed at developing a new explicit reaction mechanism for the atmospheric photooxidation of toluene is described. This mechanism is tested using experimental data from both indoor and outdoor smog chamber facilities. The predictions of the new reaction mechanism are found to be in good agreement with both sets of experimental data. Additional simulations performed with the new mechanism are used to investigate various mechanistic paths. A theoretical analysis of lumped chemical reaction mechanisms for photochemical smog is presented. Included is a description of a new counter species analysis technique which can be used to analyze any complex chemical reaction mechanism. When applied to mechanisms for photochemical smog, this analysis is shown capable of providing answers to previously inaccessible questions such as the relative contributions of individual organics to photochemical ozone formation.

Leone, J.A.

1985-01-01

181

Polarization of molecular angular momentum in the chemical reactions Li + HF and F + HD.  

PubMed

The quantum mechanical approach to vector correlation of angular momentum orientation and alignment in chemical reactions [G. Balint-Kurti and O. S. Vasyutinskii, J. Phys. Chem. A 113, 14281 (2009)] is applied to the molecular reagents and products of the Li + HF [L. Gonzalez-Sanchez, O. S. Vasyutinskii, A. Zanchet, C. Sanz-Sanz, and O. Roncero, Phys. Chem. Chem. Phys. 13, 13656 (2011)] and F + HD [D. De Fazio, J. Lucas, V. Aquilanti, and S. Cavalli, Phys. Chem. Chem. Phys. 13, 8571 (2011)] reactions for which accurate scattering information has become recently available through time-dependent and time-independent approaches. Application of the theory to two important particular cases of the reactive collisions has been considered: (i) the influence of the angular momentum polarization of reactants in the entrance channel on the spatial distribution of the products in the exit channel and (ii) angular momentum polarization of the products of the reaction between unpolarized reactants. In the former case, the role of the angular momentum alignment of the reactants is shown to be large, particularly when the angular momentum is perpendicular to the reaction scattering plane. In the latter case, the orientation and alignment of the product angular momentum was found to be significant and strongly dependent on the scattering angle. The calculation also reveals significant differences between the vector correlation properties of the two reactions under study which are due to difference in the reaction mechanisms. In the case of F + HD reaction, the branching ratio between HF and DF production points out interest in the insight gained into the detailed dynamics, when information is available either from exact quantum mechanical calculations or from especially designed experiments. Also, the geometrical arrangement for the experimental determination of the product angular momentum orientation and alignment based on a compact and convenient spherical tensor expression for the intensity of the resonance enhanced multiphoton ionization (REMPI 2 + 1) signal is suggested. PMID:23822239

Krasilnikov, Mikhail B; Popov, Ruslan S; Roncero, Octavio; De Fazio, Dario; Cavalli, Simonetta; Aquilanti, Vincenzo; Vasyutinskii, Oleg S

2013-06-28

182

Achieving Chemical Equilibrium: The Role of Imposed Conditions in the Ammonia Formation Reaction  

ERIC Educational Resources Information Center

Under conditions of constant temperature T and pressure P, chemical equilibrium occurs in a closed system (fixed mass) when the Gibbs free energy G of the reaction mixture is minimized. However, when chemical reactions occur under other conditions, other thermodynamic functions are minimized or maximized. For processes at constant T and volume V,…

Tellinghuisen, Joel

2006-01-01

183

Introducing Stochastic Simulation of Chemical Reactions Using the Gillespie Algorithm and MATLAB: Revisited and Augmented  

ERIC Educational Resources Information Center

The stochastic simulation of chemical reactions, specifically, a simple reversible chemical reaction obeying the first-order, i.e., linear, rate law, has been presented by Martinez-Urreaga and his collaborators in this journal. The current contribution is intended to complement and augment their work in two aspects. First, the simple reversible…

Argoti, A.; Fan, L. T.; Cruz, J.; Chou, S. T.

2008-01-01

184

Method of operating a thermal engine powered by a chemical reaction  

DOEpatents

The invention involves a novel method of increasing the efficiency of a thermal engine. Heat is generated by a non-linear chemical reaction of reactants, said heat being transferred to a thermal engine such as Rankine cycle power plant. The novel method includes externally perturbing one or more of the thermodynamic variables of said non-linear chemical reaction. 7 figs.

Ross, J.; Escher, C.

1988-06-07

185

Motivational Factors Contributing to Turkish High School Students' Achievement in Gases and Chemical Reactions  

ERIC Educational Resources Information Center

This study aimed to investigate the contribution of motivational factors to 10th grade students' achievement in gases and chemical reactions in chemistry. Three hundred fifty nine 10th grade students participated in the study. The Gases and Chemical Reactions Achievement Test and the Motivated Strategies for Learning Questionnaire were…

Kadioglu, Cansel; Uzuntiryaki, Esen

2008-01-01

186

Acid-Base Chemistry According to Robert Boyle: Chemical Reactions in Words as well as Symbols  

ERIC Educational Resources Information Center

Examples of acid-base reactions from Robert Boyle's "The Sceptical Chemist" are used to illustrate the rich information content of chemical equations. Boyle required lengthy passages of florid language to describe the same reaction that can be done quite simply with a chemical equation. Reading or hearing the words, however, enriches the student's…

Goodney, David E.

2006-01-01

187

Method of operating a thermal engine powered by a chemical reaction  

DOEpatents

The invention involves a novel method of increasing the efficiency of a thermal engine. Heat is generated by a non-linear chemical reaction of reactants, said heat being transferred to a thermal engine such as Rankine cycle power plant. The novel method includes externally perturbing one or more of the thermodynamic variables of said non-linear chemical reaction.

Ross, John (Stanford, CA); Escher, Claus (Nieder-Ronstadt, DE)

1988-01-01

188

Fluctuation Spectroscopy: The Determination of Chemical Reaction Rates Based on the Optical Density Fluctuation  

Microsoft Academic Search

The analysis of the half-width of the frequency spectrum due to the concentration fluctuation around the equilibrium value should give the rate constant of a chemical reaction under the appropriate condition. Specially, in a chemical reaction among the molecular species which have respectively different light absorption coefficients, the concentration fluctuations of each component molecule induce the corresponding fluctuation of the

Akiyoshi Watanabe; Yoshi-ichi Sato; Yoshito Amako

1978-01-01

189

Numerical study of chemical reactions in a surface microdischarge tube with mist flow based on experiment  

NASA Astrophysics Data System (ADS)

Recently, a water treatment method of spraying solution into a discharge region has been developed and shows high energy efficiency. In this study, a simulation model of a water treatment method using a surface microdischarge (SMD) tube with mist flow is proposed for further understanding the detailed chemical reactions. Our model has three phases (plasma, gas and liquid) and three simulation steps. The carrier gas is humid air including 2% or 3% water vapour. The chemical species diffusion characteristics in the SMD tube and the concentrations in a droplet are clarified in a wide pH interval. The simulation results show that the chemical species generated on the SMD tube inner wall are diffused to the central axis and dissolved into fine droplets. Especially, OH radicals dissolve into droplets a few mm away from the SMD tube wall because of acidification of the droplets. Furthermore, the hydrogen peroxide density, which is the most important indicator of a radical reaction in water, is influenced by the initial solution pH. This pH dependence results from ozone self-decomposition in water.

Shibata, T.; Nishiyama, H.

2014-03-01

190

Phase and chemical equilibria in the transesterification reaction of vegetable oils with supercritical lower alcohols  

NASA Astrophysics Data System (ADS)

Calculations of thermodynamic data are performed for fatty acid triglycerides, free fatty acids, and fatty acid methyl esters, participants of the transesterification reaction of vegetable oils that occurs in methanol. Using the obtained thermodynamic parameters, the phase diagrams for the reaction mixture are constructed, and the chemical equilibria of the esterification reaction of free fatty acids and the transesterification reaction of fatty acid triglycerides attained upon treatment with supercritical methanol are determined. Relying on our analysis of the obtained equilibria for the esterification reaction of fatty acids and the transesterification reaction of triglycerides attained upon treatment with lower alcohols, we select the optimum conditions for performing the reaction in practice.

Anikeev, V. I.; Stepanov, D. A.; Ermakova, A.

2011-08-01

191

Kinetic models with chemical reactions and nonequilibrium entropy in open systems  

NASA Astrophysics Data System (ADS)

Nonuniform relaxation problems are applied to simulate complex non-equilibrium processes with chemical reactions in open systems. The present paper is a continuation of our studies at a new level, in particular, 2D flows are considered. Besides the slow chemical reactions, the so-called fast reactions are studied. A special attention is paid to studying the behavior of non-equilibrium entropy and entropy flux in such complex open systems.

Aristov, Vladimir; Frolova, Anna; Zabelok, Sergey

2014-12-01

192

Mathematically Reduced Chemical Reaction Mechanism Using Neural Networks  

SciTech Connect

This is an annual technical report for the work done over the last year (period ending 9/30/2005) on the project titled ''Mathematically Reduced Chemical Reaction Mechanism Using Neural Networks''. The aim of the project is to develop an efficient chemistry model for combustion simulations. The reduced chemistry model will be developed mathematically without the need of having extensive knowledge of the chemistry involved. To aid in the development of the model, Neural Networks (NN) will be used via a new network topology know as Non-linear Principal Components Analysis (NPCA). We report on the significant development made in developing a truly meshfree computational fluid dynamics (CFD) flow solver to be coupled to NPCA. First, the procedure of obtaining nearly analytic accurate first order derivatives using the complex step method (CSM) is extended to include computation of accurate meshfree second order derivatives via a theorem described in this report. Next, boosted generalized regression neural network (BGRNN), described in our previous report is combined with CSM and used to obtain complete solution of a hard to solve wave dominated sample second order partial differential equation (PDE): the cubic Schrodinger equation. The resulting algorithm is a significant improvement of the meshfree technique of smooth particle hydrodynamics method (SPH). It is suggested that the demonstrated meshfree technique be termed boosted smooth particle hydrodynamics method (BSPH). Some of the advantages of BSPH over other meshfree methods include; it is of higher order accuracy than SPH; compared to other meshfree methods, it is completely meshfree and does not require any background meshes; It does not involve any construction of shape function with their associated solution of possibly ill conditioned matrix equations; compared to some SPH techniques, no equation for the smoothing parameter is required; finally it is easy to program.

Nelson Butuk

2006-09-21

193

DNS of a Mach 4 Boundary Layer with Chemical Reactions M. Pino Martin  

E-print Network

DNS of a Mach 4 Boundary Layer with Chemical Reactions M. Pino Mart´in Graham V. Candler Aerospace simulation (DNS) database is used to develop a greater understanding of the turbulence-chemistry interaction by endothermic reactions and destabilized by exother- mic reactions. In our previous work,2,3 we used DNS

Martín, Pino

194

A modified next reaction method for simulating chemical systems with time dependent propensities and delays  

E-print Network

A modified next reaction method for simulating chemical systems with time dependent propensities method. In this paper we make explicit use of the fact that the initiation times of the reactions can introduce our representation of the reaction times as the fir- ing times of independent,

Anderson, David F.

195

A Unified Approach to the Study of Chemical Reactions in Freshman Chemistry.  

ERIC Educational Resources Information Center

Provides rationale and objectives for presenting chemical reactions in a unified, logical six-stage approach rather than a piecemeal approach. Stages discussed include: introduction, stable electronic configurations and stable oxidation states, reactions between two free elements, ion transfer/proton transfer reactions, double displacement…

Cassen, T.; DuBois, Thomas D.

1982-01-01

196

Probing Isotope Effects in Chemical Reactions Using Single Ions  

SciTech Connect

Isotope effects in reactions between Mg{sup +} in the 3p {sup 2}P{sub 3/2} excited state and molecular hydrogen at thermal energies are studied through single reaction events. From only {approx}250 reactions with HD, the branching ratio between formation of MgD{sup +} and MgH{sup +} is found to be larger than 5. From an additional 65 reactions with H{sub 2} and D{sub 2} we find that the overall fragmentation probability of the intermediate MgH{sub 2}{sup +}, MgHD{sup +}, or MgD{sub 2}{sup +} complexes is the same. Our study shows that few single ion reactions can provide quantitative information on ion-neutral reactions. Hence, the method is well suited for reaction studies involving rare species, e.g., rare isotopes or short-lived unstable elements.

Staanum, Peter F.; Hoejbjerre, Klaus; Drewsen, Michael [QUANTOP - Danish National Research Foundation Centre for Quantum Optics, University of Aarhus, 8000 Aarhus (Denmark); Department of Physics and Astronomy, University of Aarhus, 8000 Aarhus (Denmark); Wester, Roland [Physikalisches Institut, Universitaet Freiburg, Hermann-Herder-Strasse 3, 79104 Freiburg (Germany)

2008-06-20

197

CHEMICAL SYNTHESIS USING 'GREENER' ALTERNATIVE REACTION CONDITIONS AND MEDIA  

EPA Science Inventory

The chemical research during the last decade has witnessed a paradigm shift towards "environmentally-friendly chemistry" more popularly known as "green chemistry" due to the increasing environmental concerns and legislative requirements to curb the release of chemical waste into ...

198

Chemical mechanism and kinetics study on the ocimene ozonolysis reaction in atmosphere  

NASA Astrophysics Data System (ADS)

The ocimene ozonolysis reaction is one of the most important processes for the formation of secondary organic aerosol (SOA). In this paper, molecular orbital theory has been performed for the reaction of ocimene with O 3, and the detailed reaction mechanisms of active intermediates with H 2O or NO are also presented. The geometry parameters and vibrational frequencies of the stationary points are calculated at the MPWB1K level with the 6-31G(d,p) basis set. Single-point energy calculations are carried out at the MPWB1K/6-311+G(3df,2p) level. On the basis of the quantum chemical information, the Rice-Ramsperger-Kassel-Marcus (RRKM) theory and the canonical variational transition state theory (CVT) with small-curvature tunneling effect (SCT) are used to calculate the rate constants over the temperature range of 200-800 K. The arrhenius formulas of rate constants with the temperature are fitted, which can provide helpful information for the model simulation study. The atmospheric lifetimes of the reaction species are estimated according to the rate constants.

Sun, Xiaomin; Bai, Jing; Zhao, Yuyang; Zhang, Chenxi; Wang, Yudong; Hu, Jingtian

2011-11-01

199

Reaction mechanisms of aqueous monoethanolamine with carbon dioxide: a combined quantum chemical and molecular dynamics study.  

PubMed

Aqueous monoethanolamine (MEA) has been extensively studied as a solvent for CO2 capture, yet the underlying reaction mechanisms are still not fully understood. Combined ab initio and classical molecular dynamics simulations were performed to revisit and identify key elementary reactions and intermediates in 25-30 wt% aqueous MEA with CO2, by explicitly taking into account the structural and dynamic effects. Using static quantum chemical calculations, we also analyzed in more detail the fundamental interactions involved in the MEA-CO2 reaction. We find that both the CO2 capture by MEA and solvent regeneration follow a zwitterion-mediated two-step mechanism; from the zwitterionic intermediate, the relative probability between deprotonation (carbamate formation) and CO2 removal (MEA regeneration) tends to be determined largely by the interaction between the zwitterion and neighboring H2O molecules. In addition, our calculations clearly demonstrate that proton transfer in the MEA-CO2-H2O solution primarily occurs through H-bonded water bridges, and thus the availability and arrangement of H2O molecules also directly impacts the protonation and/or deprotonation of MEA and its derivatives. This improved understanding should contribute to developing more comprehensive kinetic models for use in modeling and optimizing the CO2 capture process. Moreover, this work highlights the importance of a detailed atomic-level description of the solution structure and dynamics in order to better understand molecular mechanisms underlying the reaction of CO2 with aqueous amines. PMID:25382097

Hwang, Gyeong S; Stowe, Haley M; Paek, Eunsu; Manogaran, Dhivya

2015-01-14

200

Tattoo-Associated Skin Reaction: The Importance of an Early Diagnosis and Proper Treatment  

PubMed Central

Tattoo is going to be a very common practice especially among young people and we are witnessing a gradual increase of numerous potential complications to tattoo placement which are often seen by physicians, but generally unknown to the public. The most common skin reactions to tattoo include a transient acute inflammatory reaction due to trauma of the skin with needles and medical complications such as superficial and deep local infections, systemic infections, allergic contact dermatitis, photodermatitis, granulomatous and lichenoid reactions, and skin diseases localized on tattooed area (eczema, psoriasis, lichen, and morphea). Next to these inflammatory skin reactions we have to consider also the possibility of the development of cutaneous conditions such as pseudolymphomatous reactions and pseudoepitheliomatous hyperplasia. The aim of this study is to underline the importance of an early diagnosis by performing a histological examination especially when we are in front of suspected papulonodular lesions arising from a tattoo, followed by a proper treatment, since cutaneous neoplastic evolution is known to be a rare but possible complication. PMID:25147796

Bassi, Andrea; Campolmi, Piero; Cannarozzo, Giovanni; Conti, Rossana; Bruscino, Nicola; Gola, Massimo; Ermini, Stefano; Massi, Daniela; Moretti, Silvia

2014-01-01

201

Tattoo-associated skin reaction: the importance of an early diagnosis and proper treatment.  

PubMed

Tattoo is going to be a very common practice especially among young people and we are witnessing a gradual increase of numerous potential complications to tattoo placement which are often seen by physicians, but generally unknown to the public. The most common skin reactions to tattoo include a transient acute inflammatory reaction due to trauma of the skin with needles and medical complications such as superficial and deep local infections, systemic infections, allergic contact dermatitis, photodermatitis, granulomatous and lichenoid reactions, and skin diseases localized on tattooed area (eczema, psoriasis, lichen, and morphea). Next to these inflammatory skin reactions we have to consider also the possibility of the development of cutaneous conditions such as pseudolymphomatous reactions and pseudoepitheliomatous hyperplasia. The aim of this study is to underline the importance of an early diagnosis by performing a histological examination especially when we are in front of suspected papulonodular lesions arising from a tattoo, followed by a proper treatment, since cutaneous neoplastic evolution is known to be a rare but possible complication. PMID:25147796

Bassi, Andrea; Campolmi, Piero; Cannarozzo, Giovanni; Conti, Rossana; Bruscino, Nicola; Gola, Massimo; Ermini, Stefano; Massi, Daniela; Moretti, Silvia

2014-01-01

202

SUBSTITUTION REACTIONS FOR THE DETOXIFICATION OF HAZARDOUS CHEMICALS  

EPA Science Inventory

Chemical Treatment is one of several treatment techniques used for the remediation of toxic and hazardous chemicals. Chemical treatment in this report is defined as substitution of halogens by hydrogens for the conversion of halogenated organic toxicant into its native hydrocarb...

203

Mixing and chemical reaction in sheared and nonsheared homogeneous turbulence  

NASA Technical Reports Server (NTRS)

Direct numerical simulations were made to examine the local structure of the reaction zone for a moderately fast reaction between unmixed species in decaying, homogeneous turbulence and in a homogeneous turbulent shear flow. Pseudospectral techniques were used in domains of 64 exp 3 and higher wavenumbers. A finite-rate, single step reaction between non-premixed reactants was considered, and in one case temperature-dependent Arrhenius kinetics was assumed. Locally intense reaction rates that tend to persist throughout the simulations occur in locations where the reactant concentration gradients are large and are amplified by the local rate of strain. The reaction zones are more organized in the case of a uniform mean shear than in isotropic turbulence, and regions of intense reaction rate appear to be associated with vortex structures such as horseshoe vortices and fingers seen in mixing layers. Concentration gradients tend to align with the direction of the most compressive principal strain rate, more so in the isotropic case.

Leonard, Andy D.; Hill, James C.

1992-01-01

204

A lattice gas automata model for heterogeneous chemical reactions at mineral surfaces and in pore networks  

SciTech Connect

A lattice gas automata (LGA) model is described, which couples solute transport with chemical reactions at mineral surfaces and in pore networks. Chemical reactions and transport are integrated into a FHP-I LGA code as a module so that the approach is readily transportable to other codes. Diffusion in a box calculations are compared to finite element Fickian diffusion results and provide an approach to quantifying space-time ratios of the models. Chemical reactions at solid surfaces, including precipitation/dissolution, sorption, and catalytic reaction, can be examined with the model because solute diffusion and mineral surface processes are all treated explicitly. The simplicity and flexibility of the LGA approach provides the ability to study the interrelationship between fluid flow and chemical reactions in porous materials, at a level of complexity that has not previously been computationally possible. 20 refs., 8 figs.

Wells, J.T. (Washington Univ., Seattle, WA (USA). Dept. of Geological Sciences); Janecky, D.R.; Travis, B.J. (Los Alamos National Lab., NM (USA))

1990-01-15

205

CHEMICAL REACTIONS OF AQUATIC HUMIC MATERIALS WITH SELECTED OXIDANTS  

EPA Science Inventory

A study was conducted to identify the specific organic reaction products of natural aquatic humic materials with selected oxidants (KMnO4, HOCl, Cl02, O3 and monochloramine). Reaction products were identified by GC/MS after solvent extraction and derivatization. The two most reac...

206

Heat-Of-Reaction Chemical Heat Pumps--Possible Configurations  

E-print Network

ABSTRACT Chemical heat pumps utilize working fluids which undergo reversible chemical changes. Mechanically driven reactive heat pump cycles or, alternatively, hl~a: driven heat pumps in which either heat engine or heat pump working fluid... is reactive, are consid ~red. As such, chemical heat pumps can be classified by (a) drive (electric drive, waste heat drive, or prime energy drive), (b) operating mode (periodic or continuous), (c) type of coupling between the heat ,'ngine .1nd heat pump...

Kirol, L. D.

207

Kinetics of thermochemical gas-solid reactions important in the Venus sulfur cycle  

NASA Technical Reports Server (NTRS)

The thermochemical net reaction CaCO3 + SO2 yields CaSO4 + CO is predicted to be an important sink for incorporation of SO2 into the Venus crust. The reaction rate law was established to understand the dependence of rate on experimental variables such as temperature and partial pressure of SO2, CO2, and O2. The experimental approach was a variant of the thermogravimetric method often employed to study the kinetics of thermochemical gas-solid reactions. Clear calcite crystals were heated at constant temperature in SO2-bearing gas streams for varying time periods. Reaction rate was determined by three independent methods. A weighted linear least squares fit to all rate data yielded a rate equation. Based on the Venera 13, 14 and Vega 2 observations of CaO content of the Venus atmosphere, SO2 at the calculated rate would be removed from the Venus atmosphere in about 1,900,00 years. The most plausible endogenic source of the sulfur needed to replenish atmospheric SO2 is volcanism. The annual amount of erupted material needed for the replenishment depends on sulfur content; three ratios are used to calculate rates ranging from 0.4 to 11 cu km/year. This geochemically derived volcanism rate can be used to test if geophysically derived rates are correct. The work also suggests that Venus is less volcanically active than the Earth.

Fegley, Bruce, Jr.

1988-01-01

208

Soret and chemical reaction effects on unsteady two-dimensional natural convection along a vertical plate  

NASA Astrophysics Data System (ADS)

In this paper, a numerical solution of the unsteady two-dimensional natural convection along a vertical plate in the presence of Soret and chemical reaction effects is presented. The governing non-dimensional coupled non-linear partial differential equations have been evaluated by using an implicit finite-difference technique of Crank-Nicolson scheme. Numerical predictions for the velocity, concentration, local and average skin-friction and Sherwood number for distinct values of chemical reaction parameter and Soret number are plotted graphically. It is found that the fluid velocity and concentration decreases while increasing chemical reaction parameter whereas an increase in the Soret number increases the fluid velocity and concentration.

Raju, S. Suresh Kumar; Narahari, M.; Pendyala, Rajashekhar

2014-10-01

209

15 CFR 713.3 - Annual declaration and reporting requirements for exports and imports of Schedule 2 chemicals.  

Code of Federal Regulations, 2012 CFR

...for exports and imports of Schedule 2 chemicals. 713.3 Section 713.3 Commerce...SECURITY, DEPARTMENT OF COMMERCE CHEMICAL WEAPONS CONVENTION REGULATIONS ACTIVITIES INVOLVING SCHEDULE 2 CHEMICALS § 713.3 Annual...

2012-01-01

210

15 CFR 713.3 - Annual declaration and reporting requirements for exports and imports of Schedule 2 chemicals.  

...for exports and imports of Schedule 2 chemicals. 713.3 Section 713.3 Commerce...SECURITY, DEPARTMENT OF COMMERCE CHEMICAL WEAPONS CONVENTION REGULATIONS ACTIVITIES INVOLVING SCHEDULE 2 CHEMICALS § 713.3 Annual...

2014-01-01

211

15 CFR 713.3 - Annual declaration and reporting requirements for exports and imports of Schedule 2 chemicals.  

Code of Federal Regulations, 2011 CFR

...for exports and imports of Schedule 2 chemicals. 713.3 Section 713.3 Commerce...SECURITY, DEPARTMENT OF COMMERCE CHEMICAL WEAPONS CONVENTION REGULATIONS ACTIVITIES INVOLVING SCHEDULE 2 CHEMICALS § 713.3 Annual...

2011-01-01

212

15 CFR 713.3 - Annual declaration and reporting requirements for exports and imports of Schedule 2 chemicals.  

Code of Federal Regulations, 2010 CFR

...for exports and imports of Schedule 2 chemicals. 713.3 Section 713.3 Commerce...SECURITY, DEPARTMENT OF COMMERCE CHEMICAL WEAPONS CONVENTION REGULATIONS ACTIVITIES INVOLVING SCHEDULE 2 CHEMICALS § 713.3 Annual...

2010-01-01

213

15 CFR 713.3 - Annual declaration and reporting requirements for exports and imports of Schedule 2 chemicals.  

Code of Federal Regulations, 2013 CFR

...for exports and imports of Schedule 2 chemicals. 713.3 Section 713.3 Commerce...SECURITY, DEPARTMENT OF COMMERCE CHEMICAL WEAPONS CONVENTION REGULATIONS ACTIVITIES INVOLVING SCHEDULE 2 CHEMICALS § 713.3 Annual...

2013-01-01

214

Chemoselectivity in Chemical Biology: Acyl Transfer Reactions with Sulfur and Selenium  

PubMed Central

CONSPECTUS A critical source of insight into biological function is derived from the chemist’s ability to create new covalent bonds between molecules, whether they are endogenous or exogenous to a biological system. A daunting impediment to selective bond formation, however, is the myriad of reactive functionalities present in biological milieu. The high reactivity of the most abundant molecule in biology—water—makes the challenges all the more difficult. We have met these challenges by exploiting the reactivity of sulfur and selenium in acyl transfer reactions. The reactivity of both sulfur and selenium is high compared to that of their chalcogen congener, oxygen. In this Account, we highlight recent developments in this arena, emphasizing contributions from our laboratory. One focus of our research is furthering the chemistry of native chemical ligation (NCL) and expressed protein ligation (EPL), two related processes that enable the synthesis and semisynthesis of proteins. These techniques exploit the lower pKa of thiols and selenols relative to alcohols. Although a deprotonated hydroxyl group in the side chain of a serine residue is exceedingly rare in a biological context, the pKa value of the thiol in cysteine (8.5) and of the selenol in selenocysteine (5.7) often render these side chains anionic under physiological conditions. NCL and EPL take advantage of the high nucleophilicity of the thiolate as well as its utility as a leaving group, and we have expanded the scope of these methods to include selenocysteine. Although the genetic code limits the components of natural proteins to 20 or so ?-amino acids, NCL and EPL enable the semisynthetic incorporation of a limitless variety of nonnatural modules into proteins. These modules are enabling chemical biologists to interrogate protein structure and function with unprecedented precision. We are also pursuing the further development of the traceless Staudinger ligation, through which a phosphinothioester and azide form an amide. We first reported this chemical ligation method, which leaves no residual atoms in the product, in 2000. Our progress in effecting the reaction in water, without an organic co-solvent, was an important step in the expansion of its utility. Moreover, we have developed the traceless Staudinger reaction as a means for immobilizing proteins on a solid support, providing a general method of fabricating microarrays that display proteins in a uniform orientation. Along with NCL and EPL, the traceless Staudinger ligation has made proteins more readily accessible targets for chemical synthesis and semisynthesis. The underlying acyl transfer reactions with sulfur and selenium provide an efficient means to synthesize, remodel, and immobilize proteins, and they have enabled us to interrogate biological systems. PMID:21639109

McGrath, Nicholas A.; Raines, Ronald T.

2011-01-01

215

Students' perceptions, attitudes, and incorporation of demonstrations, popular media videos, and animations concerning chemical reactions  

NASA Astrophysics Data System (ADS)

Students often struggle with learning complex chemistry concepts. In today's society with the advances in multimedia technology, educators have a variety of tools available to help students learn these concepts. These tools include demonstrations, videos in the popular media, and animations; referred to collectively as multimethods. With the increase in possibilities educators must consider a variety of factors, the most important of which is their students. An examination of the literature leaves questions regarding the views of students as well as the impact of these tools on student learning. This study qualitatively explores student perceptions and attitudes regarding each of these multimethods using open-ended surveys, worksheets, interviews, and audio recordings. Concept maps and drawings provide insight into how students incorporate information from these multimethods into their understanding of chemical reactions. The results of the study emphasize variety for student perceptions, attitudes, conceptions, and the way they incorporate information from the multimethods. However, there also were trends in that the majority of students preferred demonstrations and the macro level. The students appeared to be aware that the use of these multimethods is designed to help them learn. Student drawings and concept maps additionally indicate a lack of understanding of the nature of chemical reactions and a failure to incorporate the information in a substantial way. Finally, implications for teaching are discussed.

Schlosser, Sarah Elizabeth

216

Fall-Off from Extrapolated Values of All Chemical Reactions at Very High Temperatures  

PubMed Central

At high temperatures the breaking of chemical bonds becomes relatively easy and the slow step in a chemical reaction shifts to the rate at which energy can seep into the bond that is to break. This has been observed by various investigators. A new general theory of reactions is developed here to explain this limiting rate at high temperatures. In the case of cyclopropane and cyclobutane the theory leads to the conclusion that 20 degrees of freedom form a heat reservoir which feeds the energy into the carbon bond that is to break and that this rate becomes controlling above about 1200°K. This would correspond to 20 of the 21 vibrational bonds of cyclopropane feeding energy into the carbon bond that is to break, and there would be no noticeable rise in the number of bonds for cyclobutane. This theory is especially important for shock tubes and detonations, where this falling-off from the extrapolated low temperature rate becomes glaringly obvious. PMID:16578725

Eyring, Henry; Leu, An-Lu

1975-01-01

217

Effect of curvature of the reaction path on dynamic effects in endothermic chemical reactions and product energies in exothermic reactions  

Microsoft Academic Search

Collinear quasiclassical trajectories are examined for two realistic potential energy surfaces for atom?diatomic molecule reactions for two reaction attributes: (1) vibrational energy of the products of a thermal?energy exothermic reaction; (2) threshold energy for endothermic reaction of ground?state reagents. Eight different mass combinations are studied. The potential energy surfaces differ primarily in the amount of potential energy released in an

James W. Duff; Donald G. Truhlar

1975-01-01

218

WATER RESOURCES RESEARCH, VOL. ???, XXXX, DOI:10.1029/, Simulation of chemical reaction via particle tracking  

E-print Network

WATER RESOURCES RESEARCH, VOL. ???, XXXX, DOI:10.1029/, Simulation of chemical reaction via/$9.00 within any single Eulerian "block" of material, the concen- trations of reactants are everywhere equal

219

EVALUATION OF CHEMICAL REACTION MECHANISMS FOR PHOTOCHEMICAL SMOG. PART 2. QUANTITATIVE EVALUATION OF THE MECHANISMS (REVISED)  

EPA Science Inventory

Six chemical reaction mechanisms for photochemical smog were analyzed to determine why, under identical conditions, they predict different maximum ozone concentrations. To perform the analysis, a counter species technique was used to determine the contributions of individual reac...

220

LSENS, a general chemical kinetics and sensitivity analysis code for gas-phase reactions: User's guide  

NASA Technical Reports Server (NTRS)

A general chemical kinetics and sensitivity analysis code for complex, homogeneous, gas-phase reactions is described. The main features of the code, LSENS, are its flexibility, efficiency and convenience in treating many different chemical reaction models. The models include static system, steady, one-dimensional, inviscid flow, shock initiated reaction, and a perfectly stirred reactor. In addition, equilibrium computations can be performed for several assigned states. An implicit numerical integration method, which works efficiently for the extremes of very fast and very slow reaction, is used for solving the 'stiff' differential equation systems that arise in chemical kinetics. For static reactions, sensitivity coefficients of all dependent variables and their temporal derivatives with respect to the initial values of dependent variables and/or the rate coefficient parameters can be computed. This paper presents descriptions of the code and its usage, and includes several illustrative example problems.

Radhakrishnan, Krishnan; Bittker, David A.

1993-01-01

221

Theoretical approach to modelling the low-barrier chemical reactions initiated by pulsed electron beam  

NASA Astrophysics Data System (ADS)

A possibility to analyze low-barrier chemical reactions induced by electron beam is proposed within the framework of generalization of classical Kramers approach. A relationship for calculation of chemical reaction rate is received for potential barriers comparable with energy of system. It has been shown that results of our approach agree with results of dynamical modeling within 2% not only in the area of applicability of classical (Kramers) approach but also more widely.

Aktaev, N. E.

2014-11-01

222

Exothermic and endothermic chemical reactions involving very many particles modeled with molecular dynamics  

Microsoft Academic Search

The traditional continuum approach of modeling chemical reactions with specified kinetic rates suffers from numerical difficulties in reactive flows and other highly non-equilibrium situations due to the stiffness of the differential equations in both space and time. These drawbacks can be eliminated within the framework of the discrete-particle approach in which the chemical reactions are modeled by means of two-body

W. Alda; D. A. Yuen; H.-P. Lüthi; J. R. Rustad

2000-01-01

223

Light-induced nitrous acid (HONO) production from NO2 heterogeneous reactions on household chemicals  

NASA Astrophysics Data System (ADS)

Nitrous acid (HONO) can be generated in various indoor environments directly during combustion processes or indirectly via heterogeneous NO2 reactions with water adsorbed layers on diverse surfaces. Indoors not only the concentrations of NO2 are higher but the surface to volume (S/V) ratios are larger and therefore the potential of HONO production is significantly elevated compared to outdoors. It has been claimed that the UV solar light is largely attenuated indoors. Here, we show that solar light (? > 340 nm) penetrates indoors and can influence the heterogeneous reactions of gas-phase NO2 with various household surfaces. The NO2 to HONO conversion mediated by light on surfaces covered with domestic chemicals has been determined at atmospherically relevant conditions i.e. 50 ppb NO2 and 50% RH. The formation rates of HONO were enhanced in presence of light for all the studied surfaces and are determined in the following order: 1.3·109 molecules cm-2 s-1 for borosilicate glass, 1.7·109 molecules cm-2 s-1 for bathroom cleaner, 1.0·1010 molecules cm-2 s-1 on alkaline detergent (floor cleaner), 1.3·1010 molecules cm-2 s-1 for white wall paint and 2.7·1010 molecules cm-2 s-1 for lacquer. These results highlight the potential of household chemicals, used for cleaning purposes to generate HONO indoors through light-enhanced NO2 heterogeneous reactions. The results obtained have been applied to predict the timely evolution of HONO in a real indoor environment using a dynamic mass balance model. A steady state mixing ratio of HONO has been estimated at 1.6 ppb assuming a contribution from glass, paint and lacquer and considering the photolysis of HONO as the most important loss process.

Gómez Alvarez, Elena; Sörgel, Matthias; Gligorovski, Sasho; Bassil, Sabina; Bartolomei, Vincent; Coulomb, Bruno; Zetzsch, Cornelius; Wortham, Henri

2014-10-01

224

Analytical solution of steady-state equations for chemical reaction networks with bilinear rate laws.  

PubMed

True steady states are a rare occurrence in living organisms, yet their knowledge is essential for quasi-steady-state approximations, multistability analysis, and other important tools in the investigation of chemical reaction networks (CRN) used to describe molecular processes on the cellular level. Here, we present an approach that can provide closed form steady-state solutions to complex systems, resulting from CRN with binary reactions and mass-action rate laws. We map the nonlinear algebraic problem of finding steady states onto a linear problem in a higher-dimensional space. We show that the linearized version of the steady-state equations obeys the linear conservation laws of the original CRN. We identify two classes of problems for which complete, minimally parameterized solutions may be obtained using only the machinery of linear systems and a judicious choice of the variables used as free parameters. We exemplify our method, providing explicit formulae, on CRN describing signal initiation of two important types of RTK receptor-ligand systems, VEGF and EGF-ErbB1. PMID:24334389

Halász, Adám M; Lai, Hong-Jian; McCabe Pryor, Meghan; Radhakrishnan, Krishnan; Edwards, Jeremy S

2013-01-01

225

ABIOTIC REDUCTION REACTIONS OF ANTHROPOGENIC ORGANIC CHEMICALS IN ANAEROBIC SYSTEMS: A CRITICAL REVIEW  

EPA Science Inventory

The review is predicated upon the need for a detailed process-level understanding of factors influencing the reduction of anthropogenic organic chemicals in natural waters. In particular, abiotic reductions of anthropogenic organic chemicals are reviewed. The most important reduc...

226

Characterisation of hydrocarbonaceous overlayers important in metal-catalysed selective hydrogenation reactions  

NASA Astrophysics Data System (ADS)

The hydrogenation of alkynes to alkenes over supported metal catalysts is an important industrial process and it has been shown that hydrocarbonaceous overlayers are important in controlling selectivity profiles of metal-catalysed hydrogenation reactions. As a model system, we have selected propyne hydrogenation over a commercial Pd(5%)/Al2O3 catalyst. Inelastic neutron scattering studies show that the C-H stretching mode ranges from 2850 to 3063 cm-1, indicating the mostly aliphatic nature of the overlayer and this is supported by the quantification of the carbon and hydrogen on the surface. There is also a population of strongly hydrogen-bonded hydroxyls, their presence would indicate that the overlayer probably contains some oxygen functionality. There is little evidence for any olefinic or aromatic species. This is distinctly different from the hydrogen-poor overlayers that are deposited on Ni/Al2O3 catalysts during methane reforming.

Lennon, David; Warringham, Robbie; Guidi, Tatiana; Parker, Stewart F.

2013-12-01

227

A technique for determining the signs of sensitivities of steady states in chemical reaction networks.  

PubMed

This paper studies the direction of change of steady states to parameter perturbations in chemical reaction networks, and, in particular, to changes in conserved quantities. Theoretical considerations lead to the formulation of a computational procedure that provides a set of possible signs of such sensitivities. The procedure is purely algebraic and combinatorial, only using information on stoichiometry, and is independent of the values of kinetic constants. Three examples of important intracellular signal transduction models are worked out as an illustration. In these examples, the set of signs found is minimal, but there is no general guarantee that the set found will always be minimal in other examples. The paper also briefly discusses the relationship of the sign problem to the question of uniqueness of steady states in stoichiometry classes. PMID:25478700

Sontag, Eduardo D

2014-12-01

228

Controllable redox reaction of chemically purified DNA-single walled carbon nanotube hybrids with hydrogen peroxide.  

PubMed

We report for the first time the controllable redox reaction of chemically purified ssDNA-HiPco SWNT hybrids with hydrogen peroxide. Compared with the suspensions before separation, the purified SWNT suspensions become inert with hydrogen peroxide which may serve as a platform for further chemical manipulation. In the presence of thiocyanate ions, the reaction of SWNTs with hydrogen peroxide is initiated and accelerated at the earlier reaction stage, accompanied with the near-infrared spectral suppression. At the later stage, the suppressed spectral intensity is recovered overtime. The thiocyanate ions may work as a mediator being able to control the reaction rate as well as the tunable properties of the reaction. The tunable redox reaction of SWNTs and H2O2 mediated by thiocyanate ions may offer a new sensing scheme for continuously monitoring H2O2 concentrations. PMID:18611008

Xu, Yang; Pehrsson, Pehr E; Chen, Liwei; Zhao, Wei

2008-08-01

229

Production of a Gas- Controlling a Chemical Reaction  

NSDL National Science Digital Library

In this activity, students have seen a few reactions that produce a gas.They will adjust the amount of baking soda and vinegar to control the amount of gas produced in the reaction. The materials needed are basic and easily available anywhere. There is a downloadable activity sheet that will be very helpful to educators, and will help students stay on track. An assessment sheet is also available on the activity page to keep track of students progress. There is also a step by step guide as to how to perform the experiment, and how to introduce it t the students.

Kessler, James; Galvan, Patti

2010-01-01

230

Femtosecond electron diffraction and spectroscopic studies of a solid state organic chemical reaction  

NASA Astrophysics Data System (ADS)

Photochromic diarylethene molecules are excellent model systems for studying electrocyclic reactions, in addition to having important technological applications in optoelectronics. The photoinduced ring-closing reaction in a crystalline photochromic diarylethene derivative was fully resolved using the complementary techniques of transient absorption spectroscopy and femtosecond electron crystallography. These studies are detailed in this thesis, together with the associated technical developments which enabled them. Importantly, the time-resolved crystallographic investigation reported here represents a highly significant proof-of-principle experiment. It constitutes the first study directly probing the molecular structural changes associated with an organic chemical reaction with sub-picosecond temporal and atomic spatial resolution---to follow the primary motions directing chemistry. In terms of technological development, the most important advance reported is the implementation of a radio frequency rebunching system capable of producing femtosecond electron pulses of exceptional brightness. The temporal resolution of this newly developed electron source was fully characterized using laser ponderomotive scattering, confirming a 435 +/- 75 fs instrument response time with 0.20 pC bunches. The ultrafast spectroscopic and crystallographic measurements were both achieved by exploiting the photoreversibility of diarylethene. The transient absorption study was first performed, after developing a novel robust acquisition scheme for thermally irreversible reactions in the solid state. It revealed the formation of an open-ring excited state intermediate, following photoexcitation of the open-ring isomer with an ultraviolet laser pulse, with a time constant of approximately 200 fs. The actual ring closing was found to occur from this intermediate with a time constant of 5.3 +/- 0.3 ps. The femtosecond diffraction measurements were then performed using multiple crystal orientations and a large number of different samples. To analyse the results, an innovative method was developed in which the apparently complex ring-closing reaction is distilled down to a small number of basic rotations. Immediately following photoexcitation, sub-picosecond structural changes associated with the formation of the intermediate are observed. The rotation of the thiophene rings is identified as the key motion. Subsequently, on the few picosecond time scale, the time-resolved diffraction patterns are observed to converge towards those associated with the closed-ring photoproduct. The formation of the closed-ring molecule is thus unambiguously witnessed.

Jean-Ruel, Hubert

231

Direct Monte Carlo simulation of chemical reaction systems: Dissociation and recombination  

E-print Network

Direct Monte Carlo simulation of chemical reaction systems: Dissociation and recombination Shannon of Physics. I. INTRODUCTION In earlier studies1­5 we have found the direct Monte Carlo simulation method6 Monte Carlo simulation of dissociation-recombination reac- tions of the type M AB M A B. These reactions

Anderson, James B.

232

Unraveling the chemical dynamics of bimolecular reactions of ground state boron atoms, B(2  

E-print Network

Unraveling the chemical dynamics of bimolecular reactions of ground state boron atoms, B(2 PjArticle on the web 8th March 2004 The reaction dynamics of atomic boron, B(2 P), with acetylene, C2H2(X 1 Sg þ molecular beams technique. Only the atomic boron versus hydrogen atom exchange pathway was observed. Forward

Kaiser, Ralf I.

233

Glow Discharge Enhanced Chemical Reaction: Application in Ammonia Synthesis and Hydrocarbon Gas Cleanup  

E-print Network

reforming ........................................................................................ 12 2.1.5 Water gas shift reaction .............................................................................. 13 2.2 Plasma physics... and thus lower the required reaction temperatures and avoid unwanted by-product formation.[9] 2.2 Plasma physics Plasma is described as the fourth state of matter. Unlike solid, liquid and gas, plasma usually character with high energy, chemical...

Ming, Pingjia

2014-06-05

234

Boundary Effects on Chaotic Advection-Diffusion Chemical Reactions M. Chertkov1  

E-print Network

rna;b a;br2na;b ÿ Rnanb; (1) where R is the reaction rate coefficient, v is the velocity of the flow chemical reaction, A B ! C, in a statistically stationary bounded chaotic flow at large Peclet number Pe lamellar structure in the bulk part of the flow is terminated by an exponential decay, / expÿt (where

Lebedev, Vladimir

235

A coupled chemical burster: The chlorine dioxide-iodide reaction in two flow reactors  

E-print Network

A coupled chemical burster: The chlorine dioxide-iodide reaction in two flow reactors Miles Dolnika (Received 13 July 1992; accepted 1 October 1992) The dynamical behavior of the chlorine dioxide, bursting behavior has been observed in the chlorine dioxide -iodide reaction in a CSTR." When the excitable

Epstein, Irving R.

236

Chemical Principles Revisited. Redox Reactions and the Electropotential Axis.  

ERIC Educational Resources Information Center

This paper suggests a nontraditional pedagogic approach to the subject of redox reactions and electrode potentials suitable for freshman chemistry. Presented is a method for the representation of galvanic cells without the introduction of the symbology and notation of conventional cell diagrams. (CW)

Vella, Alfred J.

1990-01-01

237

Theoretical studies of the dynamics of chemical reactions  

SciTech Connect

Recent research effort has focussed on several reactions pertinent to combustion. The formation of the formyl radical from atomic hydrogen and carbon monoxide, recombination of alkyl radicals and halo-alkyl radicals with halogen atoms, and the thermal dissociation of hydrogen cyanide and acetylene have been studied by modeling. In addition, the inelastic collisions of NCO with helium have been investigated.

Wagner, A.F. [Argonne National Laboratory, IL (United States)

1993-12-01

238

WORKSHOP ON STATUS OF TEST METHODS FOR ASSESSING POTENTIAL OF CHEMICALS TO INDUCE RESPIRATORY ALLERGIC REACTIONS  

EPA Science Inventory

Because of the association between allergy and asthma and the increasing incidence of morbidity and mortality due to asthma, there is growing concern over the potential of industrial chemicals to produce allergic reactions in the respiratory tract. Two classes of chemicals have b...

239

5.0 Application of Chemical Reaction Codes 5.1. Background  

E-print Network

Mineral precipitation/dissolution The distribution of aqueous species in a multi-component chemical system or more phases that includes an aqueous solution, such as the mass change resulting from the precipitation-dependent movement of one or more solutes during fluid flow. 5.2 5.1.1 Definition of Chemical Reaction Modeling

240

Trust, but verify: On the importance of chemical structure curation in cheminformatics and QSAR modeling research  

PubMed Central

Molecular modelers and cheminformaticians typically analyze experimental data generated by other scientists. Consequently, when it comes to data accuracy, cheminformaticians are always at the mercy of data providers who may inadvertently publish (partially) erroneous data. Thus, dataset curation is crucial for any cheminformatics analysis such as similarity searching, clustering, QSAR modeling, virtual screening, etc., especially nowadays when the availability of chemical datasets in public domain has skyrocketed in recent years. Despite the obvious importance of this preliminary step in the computational analysis of any dataset, there appears to be no commonly accepted guidance or set of procedures for chemical data curation. The main objective of this paper is to emphasize the need for a standardized chemical data curation strategy that should be followed at the onset of any molecular modeling investigation. Herein, we discuss several simple but important steps for cleaning chemical records in a database including the removal of a fraction of the data that cannot be appropriately handled by conventional cheminformatics techniques. Such steps include the removal of inorganic and organometallic compounds, counterions, salts and mixtures; structure validation; ring aromatization; normalization of specific chemotypes; curation of tautomeric forms; and the deletion of duplicates. To emphasize the importance of data curation as a mandatory step in data analysis, we discuss several case studies where chemical curation of the original “raw” database enabled the successful modeling study (specifically, QSAR analysis) or resulted in a significant improvement of model's prediction accuracy. We also demonstrate that in some cases rigorously developed QSAR models could be even used to correct erroneous biological data associated with chemical compounds. We believe that good practices for curation of chemical records outlined in this paper will be of value to all scientists working in the fields of molecular modeling, cheminformatics, and QSAR studies. PMID:20572635

Fourches, Denis; Muratov, Eugene; Tropsha, Alexander

2010-01-01

241

Chemical analyses of geothermal waters and Strategic Petroleum Reserve brines for metals of economic importance  

Microsoft Academic Search

Waters from seven hydrothermal-geothermal, one geopressured-geothermal, and six Strategic Petroleum Reserve wells have been surveyed for 12 metals of economic importance using trace chemical analysis techniques. The elements sought were Cr, Co, Mn, Ta, Sn, V, Nb, Li, Sr, Pt, Au and Ag. Platinum was found at a concentration of approx. 50 ppb in a brine from the Salton Sea

J. E. Harrar; E. Raber

1984-01-01

242

Control and detection of chemical reactions in microfluidic systems  

Microsoft Academic Search

Recent years have seen considerable progress in the development of microfabricated systems for use in the chemical and biological sciences. Much development has been driven by a need to perform rapid measurements on small sample volumes. However, at a more primary level, interest in miniaturized analytical systems has been stimulated by the fact that physical processes can be more easily

Andrew J. deMello

2006-01-01

243

X-ray Microspectroscopy and Chemical Reactions in Soil Microsites  

SciTech Connect

Soils provide long-term storage of environmental contaminants, which helps to protect water and air quality and diminishes negative impacts of contaminants on human and ecosystem health. Characterizing solid-phase chemical species in highly complex matrices is essential for developing principles that can be broadly applied to the wide range of notoriously heterogeneous soils occurring at the earth's surface. In the context of historical developments in soil analytical techniques, we describe applications of bulk-sample and spatially resolved synchrotron X-ray absorption spectroscopy (XAS) for characterizing chemical species of contaminants in soils, and for determining the uniqueness of trace-element reactivity in different soil microsites. Spatially resolved X-ray techniques provide opportunities for following chemical changes within soil microsites that serve as highly localized chemical micro- (or nano-)reactors of unique composition. An example of this microreactor concept is shown for micro-X-ray absorption near edge structure analysis of metal sulfide oxidation in a contaminated soil. One research challenge is to use information and principles developed from microscale soil chemistry for predicting macroscale and field-scale behavior of soil contaminants.

D Hesterberg; M Duff; J Dixon; M Vepraskas

2011-12-31

244

Chemical Reactions and Cloud Nucleation on Soot Aerosols  

NASA Astrophysics Data System (ADS)

Incomplete combustion causes enhanced levels of soot aerosols and polycyclic aromatic hydrocarbons in the urban atmosphere. In turn, the increased abundance of aerosols may facilitate increased cloudiness by acting as cloud condensation nuclei (CCN) and ice nuclei (IN). The goal of our study is to first identify and quantify chemical changes in atmospheric aerosols, such as the formation of surface hydrophilic functional groups upon exposed to ozone, and second, to assess the cloud nucleating ability of the oxidized aerosols. When first introduced into the atmosphere, soot is a hydrophobic substance and relatively poor CCN or IN. As soot encounters atmospheric oxidizing agents, such as ozone, its surface chemical properties may be altered. Thus, the soot particles become hydrophilic, and subsequently may be much more efficient cloud nuclei. In this study, soot samples are generated using various fuel sources including diesel and propane. Using a Fourier Transform Infrared Spectrometer equipped with a Horizontal Attenuated Total Reflectance cell, we observe the chemical changes at the soot surface as a function of ozone exposure. In addition, the ice nucleating ability of fresh and chemically aged soot is identified using a microscope cooling apparatus. Results will be presented and atmospheric implications discussed.

Brooks, S. D.; Mason, L.; Fornea, A.

2006-12-01

245

Development of a novel fingerprint for chemical reactions and its application to large-scale reaction classification and similarity.  

PubMed

Fingerprint methods applied to molecules have proven to be useful for similarity determination and as inputs to machine-learning models. Here, we present the development of a new fingerprint for chemical reactions and validate its usefulness in building machine-learning models and in similarity assessment. Our final fingerprint is constructed as the difference of the atom-pair fingerprints of products and reactants and includes agents via calculated physicochemical properties. We validated the fingerprints on a large data set of reactions text-mined from granted United States patents from the last 40 years that have been classified using a substructure-based expert system. We applied machine learning to build a 50-class predictive model for reaction-type classification that correctly predicts 97% of the reactions in an external test set. Impressive accuracies were also observed when applying the classifier to reactions from an in-house electronic laboratory notebook. The performance of the novel fingerprint for assessing reaction similarity was evaluated by a cluster analysis that recovered 48 out of 50 of the reaction classes with a median F-score of 0.63 for the clusters. The data sets used for training and primary validation as well as all python scripts required to reproduce the analysis are provided in the Supporting Information. PMID:25541888

Schneider, Nadine; Lowe, Daniel M; Sayle, Roger A; Landrum, Gregory A

2015-01-26

246

X-ray imaging of chemically active valence electrons during a pericyclic reaction  

NASA Astrophysics Data System (ADS)

Time-resolved imaging of chemically active valence electron densities is a long-sought goal, as these electrons dictate the course of chemical reactions. However, X-ray scattering is always dominated by the core and inert valence electrons, making time-resolved X-ray imaging of chemically active valence electron densities extremely challenging. Here we demonstrate an effective and robust method, which emphasizes the information encoded in weakly scattered photons, to image chemically active valence electron densities. The degenerate Cope rearrangement of semibullvalene, a pericyclic reaction, is used as an example to visually illustrate our approach. Our work also provides experimental access to the long-standing problem of synchronous versus asynchronous bond formation and breaking during pericyclic reactions.

Bredtmann, Timm; Ivanov, Misha; Dixit, Gopal

2014-11-01

247

X-ray imaging of chemically active valence electrons during a pericyclic reaction.  

PubMed

Time-resolved imaging of chemically active valence electron densities is a long-sought goal, as these electrons dictate the course of chemical reactions. However, X-ray scattering is always dominated by the core and inert valence electrons, making time-resolved X-ray imaging of chemically active valence electron densities extremely challenging. Here we demonstrate an effective and robust method, which emphasizes the information encoded in weakly scattered photons, to image chemically active valence electron densities. The degenerate Cope rearrangement of semibullvalene, a pericyclic reaction, is used as an example to visually illustrate our approach. Our work also provides experimental access to the long-standing problem of synchronous versus asynchronous bond formation and breaking during pericyclic reactions. PMID:25424639

Bredtmann, Timm; Ivanov, Misha; Dixit, Gopal

2014-01-01

248

Indoor volatile organic compounds and chemical sensitivity reactions.  

PubMed

Studies of unexplained symptoms observed in chemically sensitive subjects have increased the awareness of the relationship between neurological and immunological diseases due to exposure to volatile organic compounds (VOCs). However, there is no direct evidence that links exposure to low doses of VOCs and neurological and immunological dysfunction. We review animal model data to clarify the role of VOCs in neuroimmune interactions and discuss our recent studies that show a relationship between chronic exposure of C3H mice to low levels of formaldehyde and the induction of neural and immune dysfunction. We also consider the possible mechanisms by which VOC exposure can induce the symptoms presenting in patients with a multiple chemical sensitivity. PMID:24228055

Win-Shwe, Tin-Tin; Fujimaki, Hidekazu; Arashidani, Keiichi; Kunugita, Naoki

2013-01-01

249

Out-of-equilibrium catalysis of chemical reactions by electronic tunnel currents  

NASA Astrophysics Data System (ADS)

We present an escape rate theory for current-induced chemical reactions. We use Keldysh nonequilibrium Green's functions to derive a Langevin equation for the reaction coordinate. Due to the out of equilibrium electronic degrees of freedom, the friction, noise, and effective temperature in the Langevin equation depend locally on the reaction coordinate. As an example, we consider the dissociation of diatomic molecules induced by the electronic current from a scanning tunnelling microscope tip. In the resonant tunnelling regime, the molecular dissociation involves two processes which are intricately interconnected: a modification of the potential energy barrier and heating of the molecule. The decrease of the molecular barrier (i.e., the current induced catalytic reduction of the barrier) accompanied by the appearance of the effective, reaction-coordinate-dependent temperature is an alternative mechanism for current-induced chemical reactions, which is distinctly different from the usual paradigm of pumping vibrational degrees of freedom.

Dzhioev, Alan A.; Kosov, Daniel S.; von Oppen, Felix

2013-04-01

250

Experimental results of exothermic reaction with concentration gradient catalyst in a solar chemical heat pump  

SciTech Connect

Solar chemical heat pump can upgrade the low temperature solar heat about 80 C to about 150--200 C by the reversible chemical reactions of 2-propanol/acetone/hydrogen, which are composed of endothermic and exothermic reactions. In the exothermic process of above reaction, a temperature peak occurs near the inlet of reaction zone in the case of arranging catalyst uniformly. Such a temperature distribution is not suitable for heat exchange. Therefore, the authors arrange the concentration of catalyst gradationally so as not to occur the temperature peak. In this paper, experimental results of exothermic reaction with concentration gradient catalyst in a double tubular exothermic reactor are presented. These results show that the arrangement of concentration gradient catalyst has the possibility about the temperature control in the catalytic reactor.

Takashima, Takumi; Doi, Takuya; Ando, Yuji; Tanaka, Tadayoshi [Electrotechnical Lab., Tsukuba, Ibaraki (Japan); Miyahara, Ryosuke; Kamoshida, Junji [Shibaura Inst. of Tech., Omiya, Saitama (Japan)

1997-12-31

251

RPMDRATE: Bimolecular chemical reaction rates from ring polymer molecular dynamics  

NASA Astrophysics Data System (ADS)

We present RPMDRATE, a computer program for the calculation of gas phase bimolecular reaction rate coefficients using the ring polymer molecular dynamics (RPMD) method. The RPMD rate coefficient is calculated using the Bennett-Chandler method as a product of a static (centroid density quantum transition state theory (QTST) rate) and a dynamic (ring polymer transmission coefficient) factor. The computational procedure is general and can be used to treat bimolecular polyatomic reactions of any complexity in their full dimensionality. The program has been tested for the H+H2, H+CH4, OH+CH4 and H+C2H6 reactions. Catalogue identifier: AENW_v1_0 Program summary URL: http://cpc.cs.qub.ac.uk/summaries/AENW_v1_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: MIT license No. of lines in distributed program, including test data, etc.: 94512 No. of bytes in distributed program, including test data, etc.: 1395674 Distribution format: tar.gz Programming language: Fortran 90/95, Python (version 2.6.x or later, including any version of Python 3, is recommended). Computer: Not computer specific. Operating system: Any for which Python, Fortran 90/95 compiler and the required external routines are available. Has the code been vectorized or parallelized?: The program can efficiently utilize 4096+ processors, depending on problem and available computer. At low temperatures, 110 processors are reasonable for a typical umbrella integration run with an analytic potential energy function and gradients on the latest x86-64 machines.

Suleimanov, Yu. V.; Allen, J. W.; Green, W. H.

2013-03-01

252

Quantum chemical study of penicillin: Reactions after acylation  

NASA Astrophysics Data System (ADS)

The density functional theory methods were used on the model molecules of penicillin to determine the possible reactions after their acylation on ?-lactamase, and the results were compared with sulbactam we have studied. The results show that, the acylated-enzyme tetrahedral intermediate can evolves with opening of ?-lactam ring as well as the thiazole ring; the thiazole ring-open products may be formed via ?-lactam ring-open product or from tetrahedral intermediate directly. Those products, in imine or enamine form, can tautomerize via hydrogen migration. In virtue of the water-assisted, their energy barriers are obviously reduced.

Li, Rui; Feng, Dacheng; Zhu, Feng

253

Ca + HF - The anatomy of a chemical insertion reaction  

NASA Technical Reports Server (NTRS)

A comprehensive first-principles theoretical investigation of the gas phase reaction Ca + HF - CaF + H is reported. Ab initio potential energy calculations are first discussed, along with characteristics of the computed potential energy surface. Next, the fitting of the computed potential energy points to a suitable analytical functional form is described, and maps of the fitted potential surface are displayed. The methodology and results of a classical trajectory calculation utilizing the fitted potential surface are presented. Finally, the significance of the trajectory study results is discussed, and generalizations concerning dynamical aspects of Ca + HF scattering are drawn.

Jaffe, R. L.; Pattengill, M. D.; Mascarello, F. G.; Zare, R. N.

1987-01-01

254

Rate-Controlled Constrained-Equilibrium Theory of Chemical Reactions  

NASA Astrophysics Data System (ADS)

The Rate-Controlled Constrained-Equilibrium (RCCE) method for simplifying the treatment of reactions in complex systems is summarized and the selection of constraints for both close-to and far-from equilibrium systems is discussed. Illustrative examples of RCCE calculations of carbon monoxide concentrations in the exhaust products of an internal combustion engine and ignition delays for methane-oxygen mixtures in a constant volume adiabatic chamber are given and compared with "detailed" calculations. The advantages of RCCE calculations over "detailed" calculations are discussed.

Keck, James C.

2008-08-01

255

Calculation of total free energy yield as an alternative approach for predicting the importance of potential chemolithotrophic reactions in geothermal springs.  

PubMed

To inform hypotheses regarding the relative importance of chemolithotrophic metabolisms in geothermal environments, we calculated free energy yields of 26 chemical reactions potentially supporting chemolithotrophy in two US Great Basin hot springs, taking into account the effects of changing reactant and product activities on the Gibbs free energy as each reaction progressed. Results ranged from 1.2 × 10(-5) to 3.6 J kg(-1) spring water, or 3.7 × 10(-5) to 11.5 J s(-1) based on measured flow rates, with aerobic oxidation of CH(4) or NH4 + giving the highest average yields. Energy yields calculated without constraining pH were similar to those at constant pH except for reactions where H(+) was consumed, which often had significantly lower yields when pH was unconstrained. In contrast to the commonly used normalization of reaction chemical affinities per mole of electrons transferred, reaction energy yields for a given oxidant varied by several orders of magnitude and were more sensitive to differences in the activities of products and reactants. The high energy yield of aerobic ammonia oxidation is consistent with previous observations of significant ammonia oxidation rates and abundant ammonia-oxidizing archaea in sediments of these springs. This approach offers an additional lens through which to view the thermodynamic landscape of geothermal springs. PMID:22443686

Dodsworth, Jeremy A; McDonald, Austin I; Hedlund, Brian P

2012-08-01

256

Derivatisation reactions in the chromatographic analysis of chemical warfare agents and their degradation products  

Microsoft Academic Search

The analysis of chemical warfare agents and their degradation products is an important component of verification of compliance with the Chemical Weapons Convention. Gas and liquid chromatography, particularly combined with mass spectrometry, are the major techniques used to detect and identify chemicals of concern to the Convention. The more polar analytes, and some of the more reactive or highly volatile

Robin M Black; Bob Muir

2003-01-01

257

Theoretical Chemical Dynamics Studies of Elementary Combustion Reactions  

SciTech Connect

The objective of this research was to develop and apply methods for more accurate predictions of reaction rates based on high-level quantum chemistry. We have developed and applied efficient, robust methods for fitting global ab initio potential energy surfaces (PESs) for both spectroscopy and dynamics calculations and for performing direct dynamics simulations. Our approach addresses the problem that high-level quantum calculations are often too costly in computer time for practical applications resulting in the use of levels of theory that are often inadequate for reactions. A critical objective was to develop practical methods that require the minimum number of electronic structure calculations for acceptable fidelity to the ab initio PES. Our method does this by a procedure that determines the optimal configurations at which ab initio points are computed, and that ensures that the final fitted PES is uniformly accurate to a prescribed tolerance. Our fitting methods can be done automatically, with little or no human intervention, and with no prior knowledge of the topology of the PES. The methods are based on local fitting schemes using interpolating moving least-squares (IMLS). IMLS has advantages over the very effective modified-Shepard methods developed by Collins and others in that higher-order polynomials can be used and does not require derivatives but can benefit from them if available.

Donald L. Thompson

2009-09-30

258

Child-Rearing Practices toward Children with Hemophilia: The Relative Importance of Clinical Characteristics and Parental Emotional Reactions.  

ERIC Educational Resources Information Center

Addresses the relative importance of clinical characteristics of the child and parental emotional reactions, to child-rearing practices towards children with hemophilia. Results indicate that mother's emotional reactions appear to have a stronger influence on child-rearing uncertainty and overprotection than clinical characteristics of the child.…

Banis, S.; Suurmeijer, Th. P. B. M.; van Peer, D. R.

1999-01-01

259

Reaction dynamics of atomic chlorine with methane: Importance of methane bending and torsional excitation in controlling reactivity  

E-print Network

Reaction dynamics of atomic chlorine with methane: Importance of methane bending and torsional of atomic chlorine with CH4 and CD4 were studied at five collision energies ranging from 0.13 to 0.29 e-state chlorine with ground-state methane. We attribute these products to reaction of ground-state chlorine

Zare, Richard N.

260

Sensitivity of chemical reaction networks: A structural approach. 1. Examples and the carbon metabolic network.  

PubMed

In biological cells, chemical reaction pathways lead to complex network systems like metabolic networks. One experimental approach to the dynamics of such systems examines their "sensitivity": each enzyme mediating a reaction in the system is increased/decreased or knocked out separately, and the responses in the concentrations of chemicals or their fluxes are observed. In this study, we present a mathematical method, named structural sensitivity analysis, to determine the sensitivity of reaction systems from information on the network alone. We investigate how the sensitivity responses of chemicals in a reaction network depend on the structure of the network, and on the position of the perturbed reaction in the network. We establish and prove some general rules which relate the sensitivity response to the structure of the underlying network. We describe a hierarchical pattern in the flux response which is governed by branchings in the network. We apply our method to several hypothetical and real life chemical reaction networks, including the metabolic network of the Escherichia coli TCA cycle. PMID:25451520

Mochizuki, Atsushi; Fiedler, Bernold

2015-02-21

261

Small-angle neutron scattering studies of chemical reaction and reaction-induced self-assembly  

NASA Astrophysics Data System (ADS)

We have investigated a self-assembling process of cellulose artificially synthesized via enzymatic polymerization by means of in-situ and time-resolved small-angle neutron scattering (SANS). The results elucidated the following: (i) cellulose molecules were synthesized at a special reaction site of the enzyme (cellulase) located on or near the smooth surface of the self-assembled enzymes formed in the reaction medium; (ii) the synthesized molecules associated themselves via diffusion-limited aggregation (DLA) and crystallized into fibrils and (iii) the fibrils formed the aggregates, which had the surface fractal dimension Ds increasing from 2 to 2.3 with the reaction time, on the smooth surface of the enzyme aggregates.

Tanaka, H.; Koizumi, S.; Hashimoto, T.; Kurosaki, K.; Ohmae, M.; Kobayashi, S.

2006-11-01

262

Chemically Activated Formation of Organic Acids in Reactions of the Criegee Intermediate with Aldehydes and Ketones  

SciTech Connect

Reactions of the Criegee intermediate (CI, .CH2OO.) are important in atmospheric ozonolysis models. In this work, we compute the rates for reactions between .CH2OO. and HCHO, CH3CHO and CH3COCH3 leading to the formation of secondary ozonides (SOZ) and organic acids. Relative to infinitely separated reactants, the SOZ in all three cases is found to be 48–51 kcal mol-1 lower in energy, formed via 1,3- cycloaddition of .CH2OO. across the CQO bond. The lowest energy pathway found for SOZ decomposition is intramolecular disproportionation of the singlet biradical intermediate formed from cleavage of the O–O bond to form hydroxyalkyl esters. These hydroxyalkyl esters undergo concerted decomposition providing a low energy pathway from SOZ to acids. Geometries and frequencies of all stationary points were obtained using the B3LYP/MG3S DFT model chemistry, and energies were refined using RCCSD(T)-F12a/cc-pVTZ-F12 single-point calculations. RRKM calculations were used to obtain microcanonical rate coefficients (k(E)) and the reservoir state method was used to obtain temperature and pressure dependent rate coefficients (k(T, P)) and product branching ratios. At atmospheric pressure, the yield of collisionally stabilized SOZ was found to increase in the order HCHO o CH3CHO o CH3COCH3 (the highest yield being 10-4 times lower than the initial .CH2OO. concentration). At low pressures, chemically activated formation of organic acids (formic acid in the case of HCHO and CH3COCH3, formic and acetic acid in the case of CH3CHO) was found to be the major product channel in agreement with recent direct measurements. Collisional energy transfer parameters and the barrier heights for SOZ reactions were found to be the most sensitive parameters determining SOZ and organic acid yield.

Jalan, Amrit; Allen, Joshua W.; Green, William H.

2013-08-08

263

The Role of Comprehensive Detailed Chemical Kinetic Reaction Mechanisms in Combustion Research  

SciTech Connect

Recent developments by the authors in the field of comprehensive detailed chemical kinetic reaction mechanisms for hydrocarbon fuels are reviewed. Examples are given of how these mechanisms provide fundamental chemical insights into a range of combustion applications. Practical combustion consists primarily of chemical heat release from reactions between a fuel and an oxidizer, and computer simulations of practical combustion systems have become an essential tool of combustion research (Westbrook et al., 2005). At the heart of most combustion simulations, the chemical kinetic submodel frequently is the most detailed, complex and computationally costly part of a system model. Historically, the chemical submodel equations are solved using time-implicit numerical algorithms, due to the extreme stiffness of the coupled rate equations, with a computational cost that varies roughly with the cube of the number of chemical species in the model. While early mechanisms (c. 1980) for apparently simple fuels such as methane (Warnatz, 1980) or methanol (Westbrook and Dryer, 1979) included perhaps 25 species, current detailed mechanisms for much larger, more complex fuels such as hexadecane (Fournet et al., 2001; Ristori et al., 2001; Westbrook et al., 2008) or methyl ester methyl decanoate (Herbinet et al., 2008) have as many as 2000 or even 3000 species. Rapid growth in capabilities of modern computers has been an essential feature in this rapid growth in the size and complexity of chemical kinetic reaction mechanisms.

Westbrook, C K; Pitz, W J; Curran, H J; Mehl, M

2008-07-16

264

Competition between charge exchange and chemical reaction - The D2/+/ + H system  

NASA Technical Reports Server (NTRS)

Study of the special features of molecular charge exchange and its competition with chemical reaction in the case of the D2(+) + H system. The trajectory surface hopping (TSH) model proposed by Tully and Preston (1971) is used to study this competition for a number of reactions involving the above system. The diatomics-in-molecules zero-overlap approximation is used to calculate the three adiabatic surfaces - one triplet and two singlet - which are needed to describe this system. One of the significant results of this study is that the chemical reaction and charge exchange are strongly coupled. It is also found that the number of trajectories passing into the chemical regions of the three surfaces depends very strongly on the surface crossings.-

Preston, R. K.; Cross, R. J., Jr.

1973-01-01

265

Spectator Ions ARE Important! A Kinetic Study of the Copper-Aluminum Displacement Reaction  

ERIC Educational Resources Information Center

Surprisingly, spectator ions are responsible for unexpected kinetics in the biphasic copper(II)-aluminum displacement reaction, with the rate of reaction dependent on the identity of the otherwise ignored spectator ions. Application of a published kinetic analysis developed for a reaction between a rotating Al disk and a Cu(II) ion solution to the…

Sobel, Sabrina G.; Cohen, Skyler

2010-01-01

266

Mixing and chemical reaction in an idealized swirl chamber  

SciTech Connect

A vorticity-based, low-Mach-number model for simulating combustion in closed chambers is constructed. Numerical scheme is based on a mixed finite-difference pseudo-spectral discretization of the governing equations. Discrete evolution equations are integrated in time using a predictor-corrector scheme, while discrete elliptic systems are inverted with the help of fast-Poisson solver. Scheme is applied to analyze mixing and combustion in an idealized swirl cavity, which consists of the annular space between a spinning inner cylinder and a stationary reaction. To this end, we assume that the oxidizer and fuel are initially separated by a thin mixed region, and carefully control mixing levels by varying the duration of the swirl-driven mixing period. The mixture is then ignited along the boundary of the inner cylinder. When pre-mixing is complete, an axisymmetric flame front is established, and the reactants are consumed as the front propagates radially outwards. When the charge is partially mixed, combustion in the early stages predominantly occurs within a non-uniform premixed front. As this non-uniform front approaches the outer cylinder, a transition to a distributed combustion regime occurs. Following the transition, the remaining fuel burns at a slow rate within non-premixed flames which wrap around the inner cylinder. Results show that the mixing time has substantial effects on the pressure rise within the cavity and on the evolution of the burnt fraction, and that these effects become more pronounced as the Damkoehler number increases.

Knio, O.M.; Worlikar, A.S. [Johns Hopkins Univ., Baltimore, MD (United States). Dept. of Mechanical Engineering; Najm, H.N. [Sandia National Labs., Livermore, CA (United States)

1996-01-01

267

From graphite to porous carbon containing nanoparticles through chemical reactions  

SciTech Connect

Porous carbon containing large quantities of separated individual nanoparticles (2--100 nm) was produced. The chemical process includes fluorination or oxygenation of graphite, and then exposing the product (graphite fluoride or graphite oxide) to metal chlorides. The nanoparticles were metal halides or metal oxides, which could contain dopants if they were added during the synthesis process. The chlorides used in this research include those of Pd, Zn, Al and Li. Depending on the synthesis process, the carbon pores could be either filled with the nanoparticles, resulting in near-zero surface area and high metal concentration, or partially filled with nanoparticles, resulting in large surface areas. In this report, near zero surface areas were observed for a product of LiCl in carbon, and a surface area of 75 m{sup 2}/g was observed for the product of {gamma}-Al{sub 2}O{sub 3} in carbon. Heating these products in 1 atm air allowed the nanoparticles to become fused together in the form of metal oxide while the carbon was oxidized, producing metal oxides which have the same shape as the carbon precursors (fibers, fabrics, or powder) and large surface areas. These products are potentially useful in the area of batteries, high temperature gas sensors, and catalysts.

Hung, C.C. [NASA Lewis Research Center, Cleveland, OH (United States). Electro-Physics Branch; Corbin, J. [Cleveland State Univ., OH (United States). Dept. of Chemistry

1996-12-31

268

MFIX-DEM simulations of change of volumetric flow in fluidized beds due to chemical reactions  

Microsoft Academic Search

This study attempts to investigate the effect of gas volume change caused by chemical reactions on the flow hydrodynamics in a fluidized bed reactor. Various 2D simulations of ozone decomposition and the reverse reaction are conducted with a Eulerian–Lagrangian code-MFIX-DEM for a small-scale bubbling fluidized bed. The effect of particle size is studied by simulating two types of bed material

Tingwen Li; Chris Guenther

269

Dynamics of a vertically falling film in the presence of a first-order chemical reaction  

Microsoft Academic Search

The evolution of a vertically falling film in the presence of a simple first-order (exothermic or endothermic) chemical reaction is considered. The heat of reaction sets up surface tension gradients that induce thermocapillary stresses on the free-surface, thus affecting the evolution of the film. By using a long-wave expansion of the equations of motion and associated boundary conditions, we derive

Philip M. J. Trevelyan; Serafim Kalliadasis; John H. Merkin; Stephen K. Scott

2002-01-01

270

Effects of exothermic chemical reaction on the photoacoustic effect from particulate suspensions  

NASA Astrophysics Data System (ADS)

Irradiation of chemically reactive particulate suspensions by high power, pulsed laser radiation initiates reactions at the sites of the particles so that besides the absorbed optical energy, chemical energy is liberated. In addition to the release of chemical energy, chemical reaction can result in gas production both of which result in enhancement in the amplitude of the photoacoustic effect. Here we report photoacoustic and transient grating experiments with colloidal C in mixtures of H2O2 with H2O. The inclusion of H2O2 in an aqueous C suspension changes the normally endothermic reaction of C with H2O into the highly exothermic reaction of C with H2O2 leading to both an enhanced photoacoustic effect and an increase in light emission from the suspension. As well, laser-initiated exothermic reactions in suspensions of C with CH3NO2 and particulate Hg(CNO)2 in H2O are shown to result in greatly enhanced photoacoustic signal amplitudes.

Park, Han Jung; Wu, Binbin; Diebold, Gerald J.

2011-03-01

271

Effects of exothermic chemical reaction on the photoacoustic effect from particulate suspensions.  

PubMed

Irradiation of chemically reactive particulate suspensions by high power, pulsed laser radiation initiates reactions at the sites of the particles so that besides the absorbed optical energy, chemical energy is liberated. In addition to the release of chemical energy, chemical reaction can result in gas production both of which result in enhancement in the amplitude of the photoacoustic effect. Here we report photoacoustic and transient grating experiments with colloidal C in mixtures of H(2)O(2) with H(2)O. The inclusion of H(2)O(2) in an aqueous C suspension changes the normally endothermic reaction of C with H(2)O into the highly exothermic reaction of C with H(2)O(2) leading to both an enhanced photoacoustic effect and an increase in light emission from the suspension. As well, laser-initiated exothermic reactions in suspensions of C with CH(3)NO(2) and particulate Hg(CNO)(2) in H(2)O are shown to result in greatly enhanced photoacoustic signal amplitudes. PMID:21456682

Park, Han Jung; Wu, Binbin; Diebold, Gerald J

2011-03-28

272

Proposed chemical mechanisms leading to secondary organic aerosol in the reactions of aliphatic amines with hydroxyl and nitrate radicals  

NASA Astrophysics Data System (ADS)

The presence and importance of amines in the atmosphere, including aliphatic amines, continues to gain more attention. The atmospheric reaction mechanisms of these amines with key atmospheric radicals are important to predict both daytime and nighttime atmospheric chemistry. While previous studies have focused on the production of amine salts, this analysis looks at the importance of peroxy radical reactions to the formation of secondary organic aerosol. Atmospheric oxidation mechanisms are presented to explain the observed chemistry. A series of environmental chamber experiments were conducted in which aliphatic tertiary and secondary amines were reacted with either hydroxyl radical (OH) or nitrate radical (NO3). Chemical composition of the aerosol products was obtained with a High Resolution Time of Flight Aerosol Mass Spectrometer (HR-ToF-AMS) and a Particle Into Liquid Sampler Time of Flight Mass Spectrometer (PILS-ToF-MS), while the chemical composition of the gas-phase products was obtained with a Selected Ion Flow Tube Mass Spectrometer (SIFT-MS). A number of aerosol-phase mass spectra showed highly oxidized fragments at a much higher molecular weight (MW) than the amine precursor. It is proposed that these larger compounds are oligomers formed through peroxy radical reactions with hydrogen rearrangement. Another reaction pathway observed was the formation of amine salts. The relative importance of each pathway to the overall production of aerosol is found to be dependent on the type of amine and oxidant. For example, the oligomers were observed in the tertiary methyl amines, while the formation of amine salts was more prevalent in the secondary and tertiary ethyl amines.

Price, Derek J.; Clark, Christopher H.; Tang, Xiaochen; Cocker, David R.; Purvis-Roberts, Kathleen L.; Silva, Philip J.

2014-10-01

273

Chemical reactions and Schottky barrier formation at Cr\\/n-CdTe interfaces  

Microsoft Academic Search

The formation of Schottky barriers at Cr\\/n-CdTe interfaces has been investigated in detail using angle-resolved ultraviolet photo-emission, soft X-ray photo-emission and current-voltage techniques. The CdTe surfaces studied were prepared by cleaving in ultra-high vacuum, cleaving in air, and by chemical etching. The results indicate strong chemical reactions between both CdTe and its native oxide (TeO2) with evaporated Cr layers. A

I. M. Dharmadasa; M. H. Patterson; R. H. Williams

1988-01-01

274

Studies in photochemical smog chemistry. I. Atmospheric chemistry of toluene. II. Analysis of chemical reaction mechanisms for photochemical smog  

SciTech Connect

This study focuses on two related topics in the gas phase organic chemistry of importance in urban air pollution. Part I describes an experimental and modeling effort aimed at developing a new explicit reaction mechanism for the atmospheric photooxidation of toluene. This mechanism is tested using experimental data from both indoor and outdoor smog chamber facilities. The predictions of the new reaction mechanism are found to be in good agreement with both sets of experimental data. Additional simulations performed with the new mechanism are used to investigate various mechanistic paths, and to gain insight into areas where the understanding is not complete. The outdoor experimental facility, which was built to provide the second set of experimental data, consists of a 65 cubic meter teflon smog chamber together with full instrumentation capable of measuring ozone, nitrogen dioxide, nitric oxide, peroxyacetyl nitrate (PAN), carbon monoxide, relative humidity, temperature, aerosol size distributions, and of course toluene and its photooxidation products. In Part II, a theoretical analysis of lumped chemical reaction mechanisms for photochemical smog is presented. Included is a description of a new counter species analysis technique which can be used to analyze any complex chemical reaction mechanism. Finally, a new lumped mechanism for photochemical smog is developed and tested against experimental data from two smog chamber facilities. Advantages of this mechanism relative to the existing lumped mechanisms are discussed.

Leone, J.A.

1985-01-01

275

Quantum chemical approach to study the spectral properties of some important precursor of bio-molecules  

NASA Astrophysics Data System (ADS)

This work reports the spectral information of some interstellar complex molecules which could be treated as the precursor molecules for the formation of some bio-molecules in the interstellar medium (ISM). We carry out quantum chemical simulation to consider the Core correlation and vibrational corrections to the rotational constants and centrifugal distortion constants which are computed from harmonic and anharmonic force fields obtained at MP2/6-311G(d,p) level of theory. These precursor molecules could be produced in the gas phase as well as in the ice phase. This prompted use to couple the hydrodynamics of the collapsing phase of the protostar with our reasonably large chemical network including the gas phase as well as the grain phase chemical network, to study the chemical evolution of these species during the collapsing phase of a proto-star. We have noticed the Significant differences between spectroscopy of these species in the gas as well as in ice (water ice) phase due to the solute-solvent elctrostatic interactions. Time dependent density functional theory (TDDFT) is used to study the UV-VIS spectrum of these complexmolecules which are biologically important. Interstellar grain mantle around the dense cloud (> 104 cm-3) mainly composed by 60-70% Water, 5-30% Methanol and 2-20% CO2. So in reality, the ice could be mixed instead of simple water ice. To have an idea about the real spectra, we carry out our simulations for the mixed ice also by considering the actual composition of the above species in interstellar grain mantle. Spectral signatures are found to be significantly shifted with change of the solvent which confirms that the polarization of the solute by the continum has important effects on the absolute and relative solvation energies. Our simulated spectrum are in good agreement with some of the recent experimental result. We expect that our quantum chemical approach along with the hydro-chemical study might be useful for the observer to predict the abundances of some bio-molecules based on the chemical abundances of their precursor molecules.

Majumdar, Liton; Das, Ankan; Chakrabarti, Sandip K.; Chakrabarti, Sonali

2013-06-01

276

Ion-Molecule Reactions and Chemical Composition of Emanated from Herculane Spa Geothermal Sources  

PubMed Central

The paper presents a chemical composition analysis of the gases emanated from geothermal sources in the Herculane Spa area (Romania). The upper homologues of methane have been identified in these gases. An ion-molecule reaction mechanism could be implicated in the formation of the upper homologues of methane. The CH4+ ions that appear under the action of radiation are the starting point of these reactions. The presence of hydrogen in the emanated gases may be also a result of these reactions. PMID:19325844

Cosma, Constantin; Suciu, Ioan; Jäntschi, Lorentz; Bolboac?, Sorana D.

2008-01-01

277

The spliceosome catalyzes debranching in competition with reverse of the first chemical reaction  

PubMed Central

Splicing of nuclear pre-mRNA occurs via two steps of the transesterification reaction, forming a lariat intermediate and product. The reactions are catalyzed by the spliceosome, a large ribonucleoprotein complex composed of five small nuclear RNAs and numerous protein factors. The spliceosome shares a similar catalytic core structure with that of fungal group II introns, which can self-splice using the same chemical mechanism. Like group II introns, both catalytic steps of pre-mRNA splicing can efficiently reverse on the affinity-purified spliceosome. The spliceosome also catalyzes a hydrolytic spliced-exon reopening reaction as observed in group II introns, indicating a strong link in their evolutionary relationship. We show here that, by arresting splicing after the first catalytic step, the purified spliceosome can catalyze debranching of lariat-intron-exon 2. The debranching reaction, although not observed in group II introns, has similar monovalent cation preferences as those for splicing catalysis of group II introns. The debranching reaction is in competition with the reverse Step 1 reaction influenced by the ionic environment and the structure of components binding near the catalytic center, suggesting that the catalytic center of the spliceosome can switch between different conformations to direct different chemical reactions. PMID:23681507

Tseng, Chi-Kang; Cheng, Soo-Chen

2013-01-01

278

The spliceosome catalyzes debranching in competition with reverse of the first chemical reaction.  

PubMed

Splicing of nuclear pre-mRNA occurs via two steps of the transesterification reaction, forming a lariat intermediate and product. The reactions are catalyzed by the spliceosome, a large ribonucleoprotein complex composed of five small nuclear RNAs and numerous protein factors. The spliceosome shares a similar catalytic core structure with that of fungal group II introns, which can self-splice using the same chemical mechanism. Like group II introns, both catalytic steps of pre-mRNA splicing can efficiently reverse on the affinity-purified spliceosome. The spliceosome also catalyzes a hydrolytic spliced-exon reopening reaction as observed in group II introns, indicating a strong link in their evolutionary relationship. We show here that, by arresting splicing after the first catalytic step, the purified spliceosome can catalyze debranching of lariat-intron-exon 2. The debranching reaction, although not observed in group II introns, has similar monovalent cation preferences as those for splicing catalysis of group II introns. The debranching reaction is in competition with the reverse Step 1 reaction influenced by the ionic environment and the structure of components binding near the catalytic center, suggesting that the catalytic center of the spliceosome can switch between different conformations to direct different chemical reactions. PMID:23681507

Tseng, Chi-Kang; Cheng, Soo-Chen

2013-07-01

279

Measurement of Helical Trajectories in Chemical Reactions by Ion Imaging  

SciTech Connect

During the first year of this grant we developed methods to measure the sense of rotation of the nitric oxide molecule (NO) using a circularly polarized laser probe and with ion imaging detection. The method was applied to the measurement of the correlation of rotational angular momentum orientation with recoil direction in the photodissociation of NO{sub 2}. [''Detection of ''ended'' NO recoil in the 355 nm NO2 photodissociation mechanism'', V.K. Nestorov and J.I. Cline, J. Chem. Phys. 111, 5287-5290 (1999)]. The photodissociation work was performed at the University of Nevada with additional, partial support from NSF. In the summer of 1999 this technique was transported to and implemented at the Combustion Research Facility at Sandia National Laboratory in Livermore, CA in a study of rotationally inelastic collisions of NO molecules with Ar atoms. The summer 1999 experiments at Sandia demonstrated that it is possible to detect collision-induced rotational alignment (preferred planes of rotation) for product molecules. During the late summer and fall of 1999 the P.I. and student James Barr developed a theoretical method for quantifying the angular momentum alignment and for extracting it from ion images. During the winter and spring of 2000 (January-May) the P.I. was in residence at Sandia National Laboratory in Livermore during a sabbatical leave from the University of Nevada. During this time the P.I. collaborated with Sandia P.I. Dr. David Chandler and Sandia postdoctorals Thomas Lorenz and Elisabeth Wade in experiments measuring both rotational alignment and rotational orientation (preferred senses of rotation) in collisions of NO with Ar. Graduate student James Barr continued these experiments at Sandia through the end of June 2000. The success of our experimental techniques for measuring collisional alignment and the theoretical methods we have developed for extracting quantitative alignment parameters from ion images. Spectroscopic probing of products by resonance-enhanced multiphoton ionization (REMPI) detected by ion imaging is a powerful method for measuring the product state-resolved differential cross section (DCS) of bimolecular scattering reactions. Polarization of the REMPI probe light also makes imaging data potentially sensitive to product angular momentum polarization, as is well known from imaging studies of photodissociation. We exploit this sensitivity to obtain the state-resolved product angular momentum polarization as a function of recoil angle. Previous measurements of molecular angular momentum polarization in bimolecular scattering have either been constrained to detection in the scattering plane or have averaged around the azimuthal angle of the recoil velocity vector in the collision frame. Imaging detection captures the entire product recoil velocity sphere, enabling a more complete determination of product angular momentum polarization than is possible for experiments of lower detection dimensionality.

Cline, Joseph I.

2003-02-10

280

Rubber-to-metal bonding: An investigation of chemical reactions and adhesion at the interface  

NASA Astrophysics Data System (ADS)

Adhesion of rubber to steel plays an important role in many areas of technology. However, adhesion of natural rubber (NR) to most metals is poor due to the polarity of the rubber surface. In order to obtain adhesion, the substrates are often plated with brass, which is one of the few metals that NR will adhere to. The goal of this research was to elucidate the chemistry between rubber and brass at the interface and to develop primers that could replace the brass plating. Rubber fracture and model rubber experiments were used to determine the mechanisms responsible for adhesion between rubber and brass. Plasma polymerization was used to develop acetylene primers to replace brass plating. In the rubber fracture experiments, failure surfaces from rubber/brass lap joints and single wire adhesion tests were analyzed using X-ray photoelectron spectroscopy (XPS) and infrared spectroscopy (IR). It was concluded that a rubber boundary layer existed, which consisted of high levels of oxidation and silicon that were related to adhesion failure. The composition of this layer depended on cure cycle. Model rubber experiments were used to determine the effects of two vulcanization accelerators, N,N-dicyclohexyl-2-benzothiazole sulfenamide and N-tert-butyl-2-benzothiazole sulfenamide, on the reactions between rubber and brass. Squalene, a low molecular weight hydrocarbon was used in place of NR. The chemical reactions between rubber and brass were characterized by IR, Raman, and XPS analysis. Analysis of the brass substrates after reaction with the model rubber systems showed that stearates, copper oxide, and sulfides formed initially on the surface. This was followed by squalene deposition and polyene formation (crosslinking). The rates at which these reactions occurred depended on the accelerator. Plasma-polymerized acetylene primers were developed using a microwave reactor. It was determined that low levels of fragmentation of acetylene molecules led to good adhesion in the rubber/plasma film/steel system. Fragmentation was controlled by the processing parameters, such as pressure, power and flow ratio used in the deposition process. Rubber/steel lap joints prepared from steel adherends coated with plasma-polymerized acetylene films outperformed joints prepared from brass-plated steel adherends in tests of initial adhesion and durability of adhesion.

Bertelsen, Craig Michael

281

A kinetic model for chemical reactions without barriers: transport coefficients and eigenmodes  

NASA Astrophysics Data System (ADS)

The kinetic model of the Boltzmann equation proposed in the work of Kremer and Soares 2009 for a binary mixture undergoing chemical reactions of symmetric type which occur without activation energy is revisited here, with the aim of investigating in detail the transport properties of the reactive mixture and the influence of the reaction process on the transport coefficients. Accordingly, the non-equilibrium solutions of the Boltzmann equations are determined through an expansion in Sonine polynomials up to the first order, using the Chapman-Enskog method, in a chemical regime for which the reaction process is close to its final equilibrium state. The non-equilibrium deviations are explicitly calculated for what concerns the thermal-diffusion ratio and coefficients of shear viscosity, diffusion and thermal conductivity. The theoretical and formal analysis developed in the present paper is complemented with some numerical simulations performed for different concentrations of reactants and products of the reaction as well as for both exothermic and endothermic chemical processes. The results reveal that chemical reactions without energy barrier can induce an appreciable influence on the transport properties of the mixture. Oppositely to the case of reactions with activation energy, the coefficients of shear viscosity and thermal conductivity become larger than those of an inert mixture when the reactions are exothermic. An application of the non-barrier model and its detailed transport picture are included in this paper, in order to investigate the dynamics of the local perturbations on the constituent number densities, and velocity and temperature of the whole mixture, induced by spontaneous internal fluctuations. It is shown that for the longitudinal disturbances there exist two hydrodynamic sound modes, one purely diffusive hydrodynamic mode and one kinetic mode.

Alves, Giselle M.; Kremer, Gilberto M.; Marques, Wilson, Jr.; Jacinta Soares, Ana

2011-03-01

282

Charge exchange and chemical reactions with trapped Th{sup 3+}  

SciTech Connect

We have measured the reaction rates of trapped, buffer gas cooled Th{sup 3+} and various gases and have analyzed the reaction products using trapped ion mass spectrometry techniques. Ion trap lifetimes are usually limited by reactions with background molecules, and the high electron affinity of multiply charged ions such as Th{sup 3+} make them more prone to loss. Our results show that reactions of Th{sup 3+} with carbon dioxide, methane, and oxygen all occur near the classical Langevin rate, while reaction rates with argon, hydrogen, and nitrogen are orders of magnitude lower. Reactions of Th{sup 3+} with oxygen and methane proceed primarily via charge exchange, while simultaneous charge exchange and chemical reaction occurs between Th{sup 3+} and carbon dioxide. Loss rates of Th{sup 3+} in helium are consistent with reaction with impurities in the gas. Reaction rates of Th{sup 3+} with nitrogen and argon depend on the internal electronic configuration of the Th{sup 3+}.

Churchill, L. R.; DePalatis, M. V.; Chapman, M. S. [School of Physics, Georgia Institute of Technology, Atlanta, Georgia 30332-0430 (United States)

2011-01-15

283

Chemical Kinetic Data Base for Propellant Combustion I. Reactions Involving NO, NO2, HNO, HNO2, HCN and N2O  

Microsoft Academic Search

This publication contains evaluated chemical kinetic data on a number of single step elementary reactions involving small polyatomic molecules which are of importance in propellant combustion. The work involves the collection and evaluation of mechanistic and rate information and the use of various methods for the extrapolation and estimation of rate data where information does not exist. The conditions covered

Wing Tsang; John T. Herron

1991-01-01

284

The importance of checking for delayed reactions in pediatric patch testing.  

PubMed

Patch testing is often performed with the final reading being completed at 72 hours. Studies in adults have shown that performing an additional reading several days later increases the yield of relevant positive reactions. We report a study of this matter in children. We conducted a prospective patch test study of 38 affected children aged 6 to 17 (mean 11.6 years), with presumed allergic contact dermatitis between April and July 2009. The patients were required to return at 48 hours for patch test removal and assessment of early reactions, at 72 to 96 hours (3-4 days) for evaluation of delayed reactions, and again at 168 to 216 hours (7-9 days) for a final late delayed reading. We tallied the number of patients with "equivocal" (+/?), +, ++, and +++ reactions and noted these as potential positive reactions by reading date. Twenty-five of the 38 children (66%) had a positive reaction at 48 hours; 32 children (84%) had a positive reaction at 72 hours (day 3); 19 children (50%) had a positive reaction at 168 to 216 hours (day 7-9). Of those 19, 16 (42%) had persistent reactions, while 5 children (13%) had new late delayed reactions. Among the new late delayed reactions, there were six allergens identified, four of which were considered of probable clinical relevance. When patch testing with Thin Layer Rapid-Use Epicutaneous test panels, a delayed reading beyond 72 hours may be needed to identify the offending agent(s) responsible for allergic contact dermatitis in some children. Additional studies are needed to assess optimal readings schedules. PMID:21208272

Matiz, Catalina; Russell, Kathryn; Jacob, Sharon E

2011-01-01

285

A Numerical Study of Ozone Depletion and Bromine Explosion in Polar Spring Using Detailed Chemical Reaction Mechanisms  

NASA Astrophysics Data System (ADS)

Since the 1980s, it has been reported that in spring time, ozone in the polar troposphere drops from tens of ppb to a near zero value within a few days or even hours. This ozone depletion was also found to be strongly correlated to an enhancement of reactive halogen species. It is widely accepted that the reactive halogen species are involved in an auto-catalytic chemical reaction cycle, leading to the ozone depletion. Air pollution also affects ozone concentration through reactions including NOx species, in either a promotion or retardation of ozone depletion. This numerical study concerns the analysis of a detailed chemical reaction mechanism of the ozone depletion. The heterogeneous reactions of the bromine explosion are parameterized by considering an effective ice surface coverage ratio, ?, and the boundary layer height Lmix. Different values of the uptake coefficient, ?, of the BrONO2 hydrolysis reaction are investigated to study the role of nitrogen containing species. The result in Fig. 1 shows that the tropospheric ozone consumption rate depends on the boundary layer height, Lmix , and the effective surface area, ?. When the boundary layer grows from 200 to 1000 m, the ozone depletion time increases from two days to more than 20 days. If more than 10% of the ice surface act as the effective surface (? > 10%), all the curves in Fig. 1 approach the minimum limit of two days, which means the maximum ozone depletion rate caused by local chemistry is two days. During depletion, the most dominant NOx reaction cycle is related to the BrONO2 hydrolysis reaction due to the enhanced bromine in the air. A turning value of the BrONO2 uptake coefficient can be determined as ? = 0.0085 (see Fig. 2). In this situation, the ozone produced by the nitrogen cycle equals the amount of ozone destructed by the additional HOBr flux induced by nitrogen reactions. The study reveals that air pollution may influence the tropospheric ozone depletion rate, and different reaction cycles are identified, which highlights the importance of the heterogeneous reactions in ozone depletion event in tropospheric polar regions. Figure 1: Impact of effective ice surface coverage, ?, and boundary layer height, Lmix , on the ozone depletion rate Figure 2: Evolution of ozone concentration with various values of the BrONO2 uptake coefficient

Cao, L.; Gutheil, E.

2012-12-01

286

Characterization of plastic deformation and chemical reaction in titanium-polytetrafluoroethylene mixture  

Microsoft Academic Search

The subject of this dissertation is the deformation process of a single metal - polymer system (titanium - polytetrafluoroethylene) and how this process leads to initiation of chemical reaction. Several different kinds of experiments were performed to characterize the behavior of this material to shock and impact. These mechanical conditions induce a rapid plastic deformation of the sample. All of

Jeffery Jon Davis

1998-01-01

287

A Dynamical Propensity Rule for Transitions in Chemical Reactions Tamiki Komatsuzaki*, and R. Stephen Berry*,  

E-print Network

A Dynamical Propensity Rule for Transitions in Chemical Reactions Tamiki Komatsuzaki*, and R, 2002; In Final Form: July 9, 2002 A new dynamical propensity rule for transitions of a system crossing the barrier from one potential minimum to one another is derived from dynamical system theory. The rule

Berry, R. Stephen

288

Temperature-compensated chemical reactions Kanaka Rajan and L. F. Abbott  

E-print Network

Temperature-compensated chemical reactions Kanaka Rajan and L. F. Abbott Center for Neurobiology of these rhythms is that their periods remain fairly constant over a wide range of physiological temperatures, a feature called temperature compensation. Although circadian rhythms have been associated with periodic

Columbia University

289

Using Drawing Technology to Assess Students' Visualizations of Chemical Reaction Processes  

ERIC Educational Resources Information Center

In this study, we investigated how students used a drawing tool to visualize their ideas of chemical reaction processes. We interviewed 30 students using thinking-aloud and retrospective methods and provided them with a drawing tool. We identified four types of connections the students made as they used the tool: drawing on existing knowledge,…

Chang, Hsin-Yi; Quintana, Chris; Krajcik, Joseph

2014-01-01

290

Constant centrifugal potential approximation for atom-diatom chemical reaction dynamics  

E-print Network

Constant centrifugal potential approximation for atom-diatom chemical reaction dynamics Kengo,Myodaiji, Okazaki 444. Japan (Received 28 September 1993; accepted 8 December 1993) The constant centrifugal of such practically useful approxima- tions the constant centrifugal potential approximation (CCPA) (or the energy

Takada, Shoji

291

Nuclear spin selection rules in chemical reactions by angular momentum algebra  

E-print Network

Nuclear spin selection rules in chemical reactions by angular momentum algebra Takeshi Oka of the representations of the permutation­inversion group for both nuclear spin and rovibronic coordinate wavefunctions, those of the rotation group for nuclear spin wavefunction only are used. The method allows more

Oka, Takeshi

292

Lyapunov functions, stationary distributions, and non-equilibrium potential for chemical reaction networks  

E-print Network

this result to general birth-death models and demonstrate via example that similar scaling limits can yield network theory. Further, we extend this result to birth-death processes. In 1972, Horn and Jackson [16 showed that the sta- tionary distribution for the class of complex balanced chemical reaction networks

Anderson, David F.

293

DEVELOPMENT AND TESTING OF A SURROGATE SPECIES CHEMICAL REACTION MECHANISM. VOLUME 2  

EPA Science Inventory

A photochemical reaction mechanism has been updated and extensively evaluated. The testing and refinement of the surrogate species mechanism was performed in order to create an improved chemical mechanism for the atmospheric simulation models that are used to develop ozone contro...

294

DEVELOPMENT AND TESTING OF A SURROGATE SPECIES CHEMICAL REACTION MECHANISM. VOLUME 1  

EPA Science Inventory

A photochemical reaction mechanism has been updated and extensively evaluated. The testing and refinement of the surrogate species mechanism was performed in order to create an improved chemical mechanism for the atmospheric simulation models that are used to develop ozone contro...

295

Reaction ensemble molecular dynamics: Direct simulation of the dynamic equilibrium properties of chemically reacting mixtures  

E-print Network

Reaction ensemble molecular dynamics: Direct simulation of the dynamic equilibrium properties December 2004) A molecular simulation method to study the dynamics of chemically reacting mixtures for the simulation of both thermodynamic and transport properties. The method couples a molecular dynamics simulation

Lisal, Martin

296

Importance of turbulent mixing and advective transport for the chemical evolution of protoplanetary disks  

NASA Astrophysics Data System (ADS)

The understanding of the planet formation scenario requires an in-depth knowledge about the evolution of protoplanetary disks. The key process for the disk evolution is the accretion of the disk matter on a central star, which is caused by the redistribution of the angular momentum due to anomalous viscosity driven by the turbulence. While the origin of the turbulence is now close to be understood (e.g., Balbus & Hawley 1991), its basic properties, like efficiency of diffusive mixing, still remain uncertain (e.g., Brandenburg & Sokoloff 2002, Johansen & Klahr 2005). On the other hand, the global transport processes in protoplanetary disks are relatively well studied the bulk of the disk matter adjacent to midplane moves inward, thus, carrying the mass, while the rest of the disk material moves outward in the upper layer, thus, carrying the angular momentum (e.g., Keller & Gail 2004). Consequently, one may expect that the turbulent diffusion and the global transport of the matter affect to a high extent the chemical processes leading to the formation and destruction of molecules in protoplanetary disks. To study this effect, we use a 2D flared disk model with vertical temperature gradient, a 2D advection-diffusion gas-grain chemical model supplied with surface reactions, and a 2D line radiative transfer code. Using these tools, we calculate time-dependent molecular abundances, column densities, and single-dish line profiles. These results are compared with those from a static (non-mixing, non-advective) chemical model and observational data. A special emphasis is placed on the identification of the observable quantities that can be used as direct indicators for the efficiency of the turbulent mixing and advective processes in protoplanetary disks.

Semenov, Dmitry A.; Wiebe, Dmitry S.; Henning, Thomas K.; Pavlyuchenkov, Yaroslav N.

297

General chemical kinetics computer program for static and flow reactions, with application to combustion and shock-tube kinetics  

NASA Technical Reports Server (NTRS)

A general chemical kinetics program is described for complex, homogeneous ideal-gas reactions in any chemical system. Its main features are flexibility and convenience in treating many different reaction conditions. The program solves numerically the differential equations describing complex reaction in either a static system or one-dimensional inviscid flow. Applications include ignition and combustion, shock wave reactions, and general reactions in a flowing or static system. An implicit numerical solution method is used which works efficiently for the extreme conditions of a very slow or a very fast reaction. The theory is described, and the computer program and users' manual are included.

Bittker, D. A.; Scullin, V. J.

1972-01-01

298

Modeling pore collapse and chemical reactions in shock-loaded HMX crystals  

NASA Astrophysics Data System (ADS)

The localization of deformation in shock-loaded crystals of high explosive material leads to the formation of hot spots, which, if hot enough, initiate chemical reactions. The collapse of microscopic pores contained within a crystal is one such process that localizes energy and generates hot spots. Given the difficulty of resolving the details of pore collapse in shock compression experiments, it is useful to study the problem using direct numerical simulation. In this work, we focus on simulating the shock-induced closure of a single pore in crystalline ?-HMX using a multiphysics finite element code. To address coupled thermal-mechanical-chemical responses, the model incorporates a crystal-mechanics-based description of thermoelasto-viscoplasticity, the crystal melting behavior, and transformation kinetics for a single-step decomposition reaction. The model is applied to stress wave amplitudes of up to 11 GPa to study the details of pore collapse, energy localization, and the early stages of reaction initiation.

Austin, R. A.; Barton, N. R.; Howard, W. M.; Fried, L. E.

2014-05-01

299

Chemical synthesis of proanthocyanidins in vitro and their reactions in aging wines.  

PubMed

Proanthocyanidins are present in many fruits and plant products like grapes and wine, and contribute to their taste and health benefits. In the past decades of years, substantial progresses has been achieved in the identification of composition and structure of proanthocyanidins, but the debate concerning the existence of an enzymatic or nonenzymatic mechanism for proanthocyanidin condensation still goes on. Substantial attention has been paid to elucidating the potential mechanism of formation by means of biomimetic and chemical synthesis in vitro. The present paper aims at summarizing the research status on chemical synthesis of proanthocyanidins, including non-enzymatic synthesis of proanthocyanidin precursors, chemical synthesis of proanthocyanidins with direct condensation of flavanols and stereoselective synthesis of proanthocyanidins. Proanthocyanidin-involved reactions in aging wines are also reviewed such as direct and indirect reactions among proanthocyanidins, flavanols and anthocyanins. Topics for future research in this field are also put forward in this paper. PMID:19052525

He, Fei; Pan, Qiu-Hong; Shi, Ying; Duan, Chang-Qing

2008-01-01

300

Chemical kinetic analysis of hydrogen-air ignition and reaction times  

NASA Technical Reports Server (NTRS)

An anaytical study of hydrogen air kinetics was performed. Calculations were made over a range of pressure from 0.2 to 4.0 atm, temperatures from 850 to 2000 K, and mixture equivalence ratios from 0.2 to 2.0. The finite rate chemistry model included 60 reactions in 20 species of the H2-O2-N2 system. The calculations also included an assessment of how small amounts of the chemicals H2O, NOx, H2O2, and O3 in the initial mixture affect ignition and reaction times, and how the variation of the third body efficiency of H2O relative of N2 in certain key reactions may affect reaction time. The results indicate that for mixture equivalence ratios between 0.5 and 1.7, ignition times are nearly constant; however, the presence of H2O and NO can have significant effects on ignition times, depending on the mixture temperature. Reaction time is dominantly influenced by pressure but is nearly independent of initial temperature, equivalence ratio, and the addition of chemicals. Effects of kinetics on reaction at supersonic combustor conditions are discussed.

Rogers, R. C.; Schexnayder, C. J., Jr.

1981-01-01

301

Chemical synthesis of the lantibiotic lacticin 481 reveals the importance of lanthionine stereochemistry.  

PubMed

Lantibiotics are a family of antibacterial peptide natural products characterized by the post-translational installation of the thioether-containing amino acids lanthionine and methyllanthionine. Until recently, only a single naturally occurring stereochemical configuration for each of these cross-links was known. The discovery of lantibiotics with alternative lanthionine and methyllanthionine stereochemistry has prompted an investigation of its importance to biological activity. Here, solid-supported chemical synthesis enabled the total synthesis of the lantibiotic lacticin 481 and analogues containing cross-links with non-native stereochemical configurations. Biological evaluation revealed that these alterations abolished the antibacterial activity in all of the analogues, revealing the critical importance of the enzymatically installed stereochemistry for the biological activity of lacticin 481. PMID:23621626

Knerr, Patrick J; van der Donk, Wilfred A

2013-05-15

302

Modelling chemical and biological reactions during unsaturated flow in silty arable soils  

NASA Astrophysics Data System (ADS)

Ion dynamics in arable soils are strongly affected by the chemical and biological transformations triggered by fertilizer input. Hydrogeochemical models may improve our understanding of underlying processes. Our objective was to test the ability of the hydrogeochemical model PHREEQC2 in combination with the parameter optimization programme PEST to describe and predict chemical and biological processes in silty soils triggered by fertilizer application or acidification and to investigate the usefulness of different parameterization approaches. Three different experiments were carried out using undisturbed columns of two topsoils (0-25 cm) from Germany (Göttingen, GO) and from the Oman (Qasha', QA). The columns were irrigated at 10 oC with 3 mm day-1 for one year using 1 mM HCl (HCl experiment) and two fertilizer solutions with low (0.1 to 0.9 mmol L-1) and high concentrations (1.3 to 14.7 mmol L-1) of N (as NH4NO3), K, Ca and Mg. In the fertilization experiments (Fert1, Fert2), the columns were alternately irrigated with the two different solutions for variable time periods. One-dimensional transport and homogenous and heterogenous reactions were calculated using PHREEQC2. The Fert1 experiment was used for calibration. The models were validated using the Fert2 and HCl experiments. The models tested were model variant m1 with no adjustable parameters, model variant m2 in which nitrate concentrations in input solutions and cation exchange capacity were optimized for Fert1, and m3 in which additionally all cation exchange coefficients and ion concentrations in the initial solution were optimized. Model variant m1 failed to predict the concentrations of several cations for both soils (modelling efficiencies (EF) ? 0), since N dynamics were not considered adequately. Model variants m2 and m3 described (Fert1 treatment) and predicted (Fert2 and HCl treatment) pH, cation and NO3- concentrations generally more accurately for both soils. For nutrient cations, EF values for prediction for GO ranged from 0.44 (K) to 0.99 (Ca), for QA from 0.21 (K) to 0.96 (Ca). After optimization, PHREEQC2 was able to predict NO3- concentrations in both soils (EF ? 0.57). Model variant m3 indicated that between 54 (QA) and 72 % (GO) of the exchange sites were involved in cation exchange reactions. Our results show the importance of the inclusion of nitrogen species when modelling cation dynamics in arable soils from different climate regions. The hydrogeochemical model PHREEQC2 in combination with PEST was useful to describe and predict ion dynamics in silty soils under unsaturated conditions.

Michel, Kerstin; Herrmann, Sandra; Ludwig, Bernard

2010-05-01

303

Chemical Kinetic Reaction Mechanisms for Combustion of Hydrocarbon and Other Types of Chemical Fuels  

DOE Data Explorer

Reaction mechanisms have been tested and validated extensively through comparisons between computed results and measured data from laboratory experiments (e.g., shock tubes, laminar flames, rapid compression machines, flow reactors, stirred reactors) and from practical systems (e.g., diesel engines, spark-ignition engines, homogeneous charge, compression ignition (HCCI) engines). These kinetic models are used to examine a wide range of combustion systems.[Taken from https://www-pls.llnl.gov/?url=science_and_technology-chemistry-combustion

304

Chemical Reactions  

NSDL National Science Digital Library

SciPacks are 10 hour online learning experiences teachers can use to enhance their understanding of a particular scientific concept. Teachers access topics "on demand" from the Internet. Topics are based on science literacy goals in the national standards

National Science Teachers Association (NSTA)

2009-07-10

305

Chemical Reactions  

NSDL National Science Digital Library

Though titled for kids the information presented at this site is thorough and supported with hot links to related concepts as well as illustrations. Click on the blue Next Stop on the Tour button to continue learning.

2009-01-01

306

Analysis of parameter effects on transport phenomena in conjunction with chemical reactions in ducts relevant for methane reformers  

Microsoft Academic Search

Various transport phenomena in conjunction with chemical reactions are strongly affected by reformer configurations and properties of involved porous catalyst layers. The considered composite duct is relevant for a methane steam reformer and consists of a porous layer for the catalytic chemical reactions, the fuel gas flow duct and solid plate. In this paper, a fully three-dimensional calculation method is

Jinliang Yuan; XinRong Lv; Bengt Sundén; Dantin Yue

2007-01-01

307

Inducing All Steps of a Chemical Reaction with the Scanning Tunneling Microscope Tip: Towards Single Molecule Engineering  

Microsoft Academic Search

All elementary steps of a chemical reaction have been successfully induced on individual molecules with a scanning tunneling microscope (STM) in a controlled step-by-step manner utilizing a variety of manipulation techniques. The reaction steps involve the separation of iodine from iodobenzene by using tunneling electrons, bringing together two resultant phenyls mechanically by lateral manipulation and, finally, their chemical association to

Saw-Wai Hla; Ludwig Bartels; Gerhard Meyer; Karl-Heinz Rieder

2000-01-01

308

Solar photo-thermal catalytic reactions to produce high value chemicals  

SciTech Connect

This report presents a summary of the research work accomplished to date on the utilization of solar photo-thermal energy to convert low cost chemical feedstocks into high $-value chemical products. The rationale is that the solar IR-VIS-UV spectrum is unique, supplying endothermic reaction energy as well as VIS-UV for photochemical activation. Chemical market analysis and product price distribution focused attention on speciality chemicals with prices >$1.00/lb, and a synthesis sequence of n-paraffins to aromatics to partial oxidized products. The experimental work has demonstrated that enhanced reaction effects result from VIS-UV irradiation of catalytically active V2O5/SiO2. Experiments of the past year have been on dehydrogenation and dehydrocyclization of n-paraffins to olefins and aromatics with preference for the latter. Recent results using n-hexane produced 95% conversion with 56% benzene; it is speculated that aromatic yield should reach {approximately}70% by further optimization. Pilot- and commercial-scale reactor configurations have been examined; the odds-on-favorite being a shallow fluid-bed of catalyst with incident radiation from the top. Sequencing for maximum cost effectiveness would be day-time endothermic followed by night-time exothermic reactions to produce the products.

Prengle, H.W. Jr.; Wentworth, W.E. (Houston Univ., TX (United States))

1992-04-01

309

The swelling behavior of ionic polymers in the presence of diffusion and chemical reactions  

NASA Astrophysics Data System (ADS)

During the past few decades, ionic polymers have attracted much attention due to their unique properties, i.e., a stimulus-sensitive swelling behavior. The use of ionic polymers in biotechnology and medicine is increasingly attractive for applications such as controlled drug delivery, biomimetic actuators, and chemical valves. The ability to model and predict the swelling behavior of polymers and mass flux with respect to external environmental conditions is very important in such applications. The focus of this dissertation is on developing a continuum model for the behavior of a swollen solid and diffusion of a fluid through it in the presence of chemical reactions. To model diffusion through an ionic/nonionic polymer in the presence of mechanical deformation, we develop a variational procedure based on a thermodynamic framework for a swollen solid subject to constraints. This thermodynamic framework was mainly developed by Rajagopal and Srinivasa as a general thermodynamic framework for inelastic behavior of materials. First, a model for the mechanical behavior of a rubber-like solid in the presence of mass diffusion is developed using the variational procedure. By assuming a specific form for the Helmholtz potential function, we obtain an equilibrium equation that is identical to the equation suggested by Flory, Huggins, and Rehner. For the non-equilibrium problem, we assume a specific form for the rate of dissipation function and obtain the relation between pressure difference and mass flux. The numerical results show very good agreement with experimental data for the diffusion of organic solvents through a rubber slab. Hysteresis response of the swollen solid due to time-dependent loads is also simulated by the model. The variational procedure is also applied to pH-sensitive ionic polymers, which not only yields the equations for the deformation of a swollen solid and mass flux, but also the equations for chemical equilibrium. As a specific example, an anionic polymer containing carboxylic acid in a solution of NaOH is investigated and its behavior in solutions of different pH and surrounding pressures is predicted. The numerical results show good agreement with the experimental data.

Baek, Seungik

310

Investigation of shock-induced and shock-assisted chemical reactions in molybdenum-silicon powder mixtures  

NASA Astrophysics Data System (ADS)

In this research, chemical reactions occurring in molybdenum and silicon powder mixtures under "shock-induced" (those occurring during the high-pressure shock state) and "shock-assisted" (those occurring subsequent to the shock event, but due to bulk temperature increases) conditions were investigated. Differences in the densities and yield strengths of the two constituents, in addition to the large heat of reaction associated with molybdenum disilicide (MoSi2) formation can lead to shock-induced as well as shock-assisted reactions, which make this an ideal system to delineate the kinetics and mechanisms of reactions occurring in shock-compressed powder mixtures. Shock recovery experiments performed on Mo + 2 Si powder mixtures employing cylindrical implosion geometry showed thermally initiated reactions. A mixed phase eutectic type microstructure of MoSi2 and Mo 5Si3, resulting from reaction occurring due to melting of both reactants, was observed in axial regions of the cylindrical compacts. In regions surrounding the mach stem, melting of only silicon and reaction occurring via dissolution and re-precipitation forming MoSi2 spherules surrounding molybdenum particles in a melted and solidified silicon matrix was observed. The planar pressure shock recovery geometry showed a single phase MoSi2, microstructure formed due to a solid-state pressure-induced reaction process. The time-resolved instrumented experiments were performed using a single stage gas gun in the velocity range of 500 m/s to 1 km/s, and employed poly-vinyl di-flouride (PVDF) stress gauges placed at the front and rear surfaces of the powder to determine the crush strength, densification history, and reaction initiation threshold conditions. Time-resolved experiments performed on ˜58% dense Mo + 2 Si powder mixtures at input stresses less than 4 GPa, showed characteristics of powder densification and dispersed propagated wave stress profiles with rise time >˜40 nanoseconds. At input stress between 4--6 GPa, the powder mixtures showed a sharp rise time (<˜10 ns) of propagated wave profile and an expanded state of products revealing conclusive evidence of shock-induced reaction. At input stresses greater than 6 GPa, the powder mixtures showed a lower rise time and transition to a low-compressibility (melt) state indicating lack of shock-induced reaction. The results of this work show that (a) premature formation of a melt phase restricts mixing between reactants and inhibits "shock-induced" reaction initiation, although "shock-assisted" reactions can still occur in time scales of thermal equilibrium, and (b) the crush strength of powder mixtures is the most important parameter that controls initiation of a "shock-induced" reaction. Reaction synthesis experiments conducted on 55--95% dense Mo + 2 Si powder mixture compacts under an applied electric field showed that SHS reactions that would have normally become extinguished without the application of electric field, were observed to be self-sustained. Under such conditions, the reaction kinetics were observed to be enhanced and the reaction products showed a highly refined microstructure.

Vandersall, Kevin Stewart

1999-10-01

311

A Non-Orthogonal Block-Localized Effective Hamiltonian Approach for Chemical and Enzymatic Reactions  

PubMed Central

The effective Hamiltonian-molecular orbital and valence bond (EH-MOVB) method based on non-orthogonal block-localized fragment orbitals has been implemented into the program CHARMM for molecular dynamics simulations of chemical and enzymatic reactions, making use of semiempirical quantum mechanical models. Building upon ab initio MOVB theory, we make use of two parameters in the EH-MOVB method to fit the barrier height and the relative energy between the reactant and product state for a given chemical reaction to be in agreement with experiment or high-level ab initio or density functional results. Consequently, the EH-MOVB method provides a highly accurate and computationally efficient QM/MM model for dynamics simulation of chemical reactions in solution. The EH-MOVB method is illustrated by examination of the potential energy surface of the hydride transfer reaction from trimethylamine to a flavin cofactor model in the gas phase. In the present study, we employed the semiempirical AM1 model, which yields a reaction barrier that is more than 5 kcal/mol too high. We use a parameter calibration procedure for the EH-MOVB method similar to that employed to adjust the results of semiempirical and empirical models. Thus, the relative energy of these two diabatic states can be shifted to reproduce the experimental energy of reaction, and the barrier height is optimized to reproduce the desired (accurate) value by adding a constant to the off-diagonal matrix element. The present EH-MOVB method offers a viable approach to characterizing solvent and protein-reorganization effects in the realm of combined QM/MM simulations. PMID:20694172

Cembran, Alessandro; Payaka, Apirak; Lin, Yen-lin; Xie, Wangshen; Mo, Yirong; Song, Lingchun; Gao, Jiali

2010-01-01

312

Open chemical reaction networks, steady-state loads and Braess-like paradox  

E-print Network

Open chemical reaction systems involve matter-exchange with the surroundings. As a result, species can accumulate inside a system during the course of the reaction. We study the role of network topology in governing the concentration build-up inside a fixed reaction volume at steady state, particularly focusing on the effect of additional paths. The problem is akin to that in traffic networks where an extra route, surprisingly, can increase the overall travel time. This is known as the Braess' paradox. Here, we report chemical analogues of such a paradox in suitably chosen reaction networks, where extra reaction step(s) can inflate the total concentration, denoted as `load', at steady state. It is shown that, such counter-intuitive behavior emerges in a qualitatively similar pattern in networks of varying complexities. We then explore how such extra routes affect the load in a biochemical scheme of uric acid degradation. From a thorough analysis of this network, we propose a functional role of some decomposit...

Banerjee, Kinshuk

2014-01-01

313

Simulations of isoprene: Ozone reactions for a general circulation/chemical transport model  

NASA Technical Reports Server (NTRS)

A parameterized reaction mechanism has been created to examine the interactions between isoprene and other tropospheric gas-phase chemicals. Tests of the parameterization have shown that its results match those of a more complex reaction set to a high degree of accuracy. Comparisons between test runs have shown that the presence of isoprene at the start of a six day interval can enhance later ozone concentrations by as much as twenty-nine percent. The test cases used no input fluxes beyond the initial time, implying that a single input of a biogenic hydrocarbon to an airmass can alter its ozone chemistry over a time scale on the order of a week.

Makar, P. A.; Mcconnell, J. C.

1994-01-01

314

Influence of Alumina Reaction Tube Impurities on the Oxidation of Chemically-Vapor-Deposited Silicon Carbide  

NASA Technical Reports Server (NTRS)

Pure coupons of chemically vapor deposited (CVD) SiC were oxidized for 100 h in dry flowing oxygen at 1300 C. The oxidation kinetics were monitored using thermogravimetry (TGA). The experiments were first performed using high-purity alumina reaction tubes. The experiments were then repeated using fused quartz reaction tubes. Differences in oxidation kinetics, scale composition, and scale morphology were observed. These differences were attributed to impurities in the alumina tubes. Investigators interested in high-temperature oxidation of silica formers should be aware that high-purity alumina can have significant effects on experiment results.

Opila, Elizabeth

1995-01-01

315

Computational studies of atmospherically-relevant chemical reactions in water clusters and on liquid water and ice surfaces.  

PubMed

Conspectus Reactions on water and ice surfaces and in other aqueous media are ubiquitous in the atmosphere, but the microscopic mechanisms of most of these processes are as yet unknown. This Account examines recent progress in atomistic simulations of such reactions and the insights provided into mechanisms and interpretation of experiments. Illustrative examples are discussed. The main computational approaches employed are classical trajectory simulations using interaction potentials derived from quantum chemical methods. This comprises both ab initio molecular dynamics (AIMD) and semiempirical molecular dynamics (SEMD), the latter referring to semiempirical quantum chemical methods. Presented examples are as follows: (i) Reaction of the (NO(+))(NO3(-)) ion pair with a water cluster to produce the atmospherically important HONO and HNO3. The simulations show that a cluster with four water molecules describes the reaction. This provides a hydrogen-bonding network supporting the transition state. The reaction is triggered by thermal structural fluctuations, and ultrafast changes in atomic partial charges play a key role. This is an example where a reaction in a small cluster can provide a model for a corresponding bulk process. The results support the proposed mechanism for production of HONO by hydrolysis of NO2 (N2O4). (ii) The reactions of gaseous HCl with N2O4 and N2O5 on liquid water surfaces. Ionization of HCl at the water/air interface is followed by nucleophilic attack of Cl(-) on N2O4 or N2O5. Both reactions proceed by an SN2 mechanism. The products are ClNO and ClNO2, precursors of atmospheric atomic chlorine. Because this mechanism cannot result from a cluster too small for HCl ionization, an extended water film model was simulated. The results explain ClNO formation experiments. Predicted ClNO2 formation is less efficient. (iii) Ionization of acids at ice surfaces. No ionization is found on ideal crystalline surfaces, but the process is efficient on isolated defects where it involves formation of H3O(+)-acid anion contact ion pairs. This behavior is found in simulations of a model of the ice quasi-liquid layer corresponding to large defect concentrations in crystalline ice. The results are in accord with experiments. (iv) Ionization of acids on wet quartz. A monolayer of water on hydroxylated silica is ordered even at room temperature, but the surface lattice constant differs significantly from that of crystalline ice. The ionization processes of HCl and H2SO4 are of high yield and occur in a few picoseconds. The results are in accord with experimental spectroscopy. (v) Photochemical reactions on water and ice. These simulations require excited state quantum chemical methods. The electronic absorption spectrum of methyl hydroperoxide adsorbed on a large ice cluster is strongly blue-shifted relative to the isolated molecule. The measured and calculated adsorption band low-frequency tails are in agreement. A simple model of photodynamics assumes prompt electronic relaxation of the excited peroxide due to the ice surface. SEMD simulations support this, with the important finding that the photochemistry takes place mainly on the ground state. In conclusion, dynamics simulations using quantum chemical potentials are a useful tool in atmospheric chemistry of water media, capable of comparison with experiment. PMID:25647299

Gerber, R Benny; Varner, Mychel E; Hammerich, Audrey D; Riikonen, Sampsa; Murdachaew, Garold; Shemesh, Dorit; Finlayson-Pitts, Barbara J

2015-02-17

316

A Microscale Approach to Chemical Kinetics in the General Chemistry Laboratory: The Potassium Iodide Hydrogen Peroxide Iodine-Clock Reaction  

ERIC Educational Resources Information Center

A microscale laboratory for teaching chemical kinetics utilizing the iodine clock reaction is described. Plastic pipets, 3 mL volume, are used to store and deliver precise drops of reagents and the reaction is run in a 24 well plastic tray using a total 60 drops of reagents. With this procedure, students determine the rate of reaction and the…

Sattsangi, Prem D.

2011-01-01

317

Analysis of chemical-reaction-coupled mass and heat transport phenomena in a methane reformer duct for PEMFCs  

Microsoft Academic Search

Mass, heat and momentum transport processes are coupled with catalytic chemical reactions in a methane steam reforming duct. It is often found that endothermic and exothermic reactions in the ducts are strongly integrated by heat transfer from adjacent catalytic combustion ducts. In this paper, a three-dimensional calculation method is developed to simulate and analyze reforming reactions of methane, and the

Jinliang Yuan; Fuan Ren; Bengt Sundén

2007-01-01

318

SCRIPDB: a portal for easy access to syntheses, chemicals and reactions in patents  

PubMed Central

The patent literature is a rich catalog of biologically relevant chemicals; many public and commercial molecular databases contain the structures disclosed in patent claims. However, patents are an equally rich source of metadata about bioactive molecules, including mechanism of action, disease class, homologous experimental series, structural alternatives, or the synthetic pathways used to produce molecules of interest. Unfortunately, this metadata is discarded when chemical structures are deposited separately in databases. SCRIPDB is a chemical structure database designed to make this metadata accessible. SCRIPDB provides the full original patent text, reactions and relationships described within any individual patent, in addition to the molecular files common to structural databases. We discuss how such information is valuable in medical text mining, chemical image analysis, reaction extraction and in silico pharmaceutical lead optimization. SCRIPDB may be searched by exact chemical structure, substructure or molecular similarity and the results may be restricted to patents describing synthetic routes. SCRIPDB is available at http://dcv.uhnres.utoronto.ca/SCRIPDB. PMID:22067445

Heifets, Abraham; Jurisica, Igor

2012-01-01

319

Self-propelled motion of a fluid droplet under chemical reaction  

NASA Astrophysics Data System (ADS)

We study self-propelled dynamics of a droplet due to a Marangoni effect and chemical reactions in a binary fluid with a dilute third component of chemical product which affects the interfacial energy of a droplet. The equation for the migration velocity of the center of mass of a droplet is derived in the limit of an infinitesimally thin interface. We found that there is a bifurcation from a motionless state to a propagating state of droplet by changing the strength of the Marangoni effect.

Yabunaka, S.; Ohta, T.; Yoshinaga, N.

2012-02-01

320

Numerical simulation of the interaction of transport, diffusion and chemical reactions in an urban plume  

NASA Technical Reports Server (NTRS)

A model system is presented that takes into account the main physical and chemical processes on the regional scale here in an area of 100x100 sq km. The horizontal gridsize used is 2x2 sq km. For a case study, it is demonstrated how the model system can be used to separate the contributions of the processes advection, turbulent diffusion, and chemical reactions to the diurnal cycle of ozone. In this way, typical features which are visible in observations and are reproduced by the numerical simulations can be interpreted.

Vogel, Bernhard; Vogel, Heike; Fiedler, Franz

1994-01-01

321

Multivariate Population Balances via Moment and Monte Carlo Simulation Methods: An Important Sol Reaction Engineering  

E-print Network

Multivariate Population Balances via Moment and Monte Carlo Simulation Methods: An Important Sol with a population balance equation governing evolution of the "dispersed" (suspended) particle population. Early, hopefully, motivate a broader attack on important multivariate population balance problems, including those

322

Importance of structural and chemical heterogeneity of activated carbon surfaces for adsorption of dibenzothiophene  

SciTech Connect

The performance of various activated carbons obtained from different carbon precursors (i.e., plastic waste, coal, and wood) as adsorbents for the desulfurization of liquid hydrocarbon fuels was evaluated. To increase surface heterogeneity, the carbon surface was modified by oxidation with ammonium persulfate. The results showed the importance of activated carbon pore sizes and surface chemistry for the adsorption of dibenzothiophene (DBT) from liquid phase. Adsorption of DBT on activated carbons is governed by two types of contributions: physical and chemical interactions. The former include dispersive interactions in the microporous network of the carbons. While the volume of micropores governs the amount physisorbed, mesopores control the kinetics of the process. On the other hand, introduction of surface functional groups enhances the performance of the activated carbons as a result of specific interactions between the acidic centers of the carbon and the basic structure of DBT molecule as well as sulfur-sulfur interactions.

Ania, C.O.; Bandosz, T.J. [CUNY City College, New York, NY (United States). Dept. of Chemistry

2005-08-16

323

The Q-K model for gas-phase chemical reaction rates  

NASA Astrophysics Data System (ADS)

The quantum-kinetic, or Q-K, model is based on the quantum vibration model that is employed in the computation of gas flows at the molecular level by the direct simulation Monte Carlo (DSMC) method. The Q-K procedure for dissociation is physically realistic within the context of the vibration model in that the reaction occurs upon the selection of the vibrational level that corresponds to dissociation. An analogous, but entirely phenomenological, procedure has been presented for endothermic exchange and chain reactions. These procedures for the endothermic reactions have been well validated, but the existing procedures for the corresponding exothermic reactions have proved to be problematic. This paper presents new procedures for the exothermic reactions that are computationally efficient and provide a near exact match with the equilibrium constant of statistical mechanics. The Q-K model does not depend on the availability of continuum rate coefficients. Instead, the simplicity of the new DSMC procedures allows analytical expressions to be written down for the corresponding rate coefficients in an equilibrium gas. These are used to validate the Q-K model for reactions in high temperature air and in hydrogen-oxygen combustion. The development of the Q-K model has been driven by the need for efficient reaction procedures in DSMC applications that often involve the computation of billions of simulated collisions. It is not intended to compete with the modern theories for gas-phase chemical reactions that employ more accurate physical representations of real reactions. At the same time, the degree of validation of the model is such that the analytical expressions for the rate coefficients that correspond to the model should be useful in their own right.

Bird, G. A.

2011-10-01

324

Role of impact parameter in branching reactions: Chemical accelerator studies of the reaction Xe++CH4?XeCH3 ++H  

E-print Network

Integral reaction cross sections and product velocity distributions have been measured for the ion–molecule reaction Xe+(CH4,H)XeCH3 + over the relative reactant translational energy range of 0.7–5.5 eV by chemical accelerator techniques...

Miller, G. D.; Strattan, L. W.; Hierl, Peter M.

1981-01-01

325

Laboratory studies of sticking coefficients and heterogeneous reactions important in the Antarctic stratosphere  

NASA Technical Reports Server (NTRS)

Laboratory studies of sticking coefficients of H2O, HCl, Cl2, and HNO3 on ice and heterogeneous reactions of ClONO2 with ice or HCl/ice have been performed in a fast flow reactor. A quadrupole mass spectrometer with electron impact ionization was used as a detector. Measured sticking coefficients are: 0.3 (+0.7, -0.1) for H2O, 0.4 (+0.6, -0.2) for HCL, less than 0.0001 for Cl2, and 0.3 (+0.7, -0.1) for HNO3 at 200 K. The reaction probability of ClONO2 on ice was found to be 0.06 (+ or - 0.03) while HOCl was observed as a sole product in the gas phase. With HCl present in ice, the reaction probability of ClONO2 is greatly enhanced, approaching 0.27 (+0.73, -0.13) while molecular chlorine was found to be the major product in the gas phase. Another reaction product was nitric acid which remained in the solid phase. Since the polar stratospheric clouds contain ice particles or possibly HCl/ice particles on the surface, the present results should be a major factor in producing the observed springtime ozone depletion in the Antarctic stratosphere.

Leu, Ming-Taun

1988-01-01

326

Identification of amino acid residues important in the cyclization reactions of chalcone and stilbene synthases.  

PubMed Central

Chalcone synthase (CHS) and stilbene synthase (STS) catalyse condensation reactions of p-coumaroyl-CoA and three C(2) units from malonyl-CoA up to a common tetraketide intermediate but then catalyse different cyclization reactions to produce naringenin chalcone and resveratrol respectively. On the basis of sequence alignment with other condensing enzymes including 3-ketoacyl-(acyl carrier protein) synthases of polyketide and fatty-acid synthases, site-directed mutagenesis was performed on the active-site G(372)FGPG loops in CHS and STS. The CHS-P375G mutant showed a 6-fold decrease in overall condensing activity with selectively increased production of p-coumaroyltriacetic acid lactone (CTAL, the derailment product of the tetraketide intermediate). Meanwhile, resveratrol production by STS-P(375)G strongly decreased to give various products in the order CTAL> resveratrol approximately bisnoryangonin>naringenin. As a result, naringenin production (cross-reaction) by STS-P(375)G was close to 30% of resveratrol production. Both G(374)L mutants of CHS and STS showed no condensing activity with residual malonyl-CoA decarboxylase activity. These results suggested that the G(372)FGPG loop in CHS and STS contribute to a determination of the outcome during cyclization reactions by serving as a part of the active-site scaffold on which the stereochemistry of cyclization is performed. These observations provide the first biochemical indication that cyclization reactions are modulated by active-site geometry. The implications for the evolutionary relationship of these enzymes are also discussed. PMID:10926848

Suh, D Y; Fukuma, K; Kagami, J; Yamazaki, Y; Shibuya, M; Ebizuka, Y; Sankawa, U

2000-01-01

327

Identification of amino acid residues important in the cyclization reactions of chalcone and stilbene synthases.  

PubMed

Chalcone synthase (CHS) and stilbene synthase (STS) catalyse condensation reactions of p-coumaroyl-CoA and three C(2) units from malonyl-CoA up to a common tetraketide intermediate but then catalyse different cyclization reactions to produce naringenin chalcone and resveratrol respectively. On the basis of sequence alignment with other condensing enzymes including 3-ketoacyl-(acyl carrier protein) synthases of polyketide and fatty-acid synthases, site-directed mutagenesis was performed on the active-site G(372)FGPG loops in CHS and STS. The CHS-P375G mutant showed a 6-fold decrease in overall condensing activity with selectively increased production of p-coumaroyltriacetic acid lactone (CTAL, the derailment product of the tetraketide intermediate). Meanwhile, resveratrol production by STS-P(375)G strongly decreased to give various products in the order CTAL> resveratrol approximately bisnoryangonin>naringenin. As a result, naringenin production (cross-reaction) by STS-P(375)G was close to 30% of resveratrol production. Both G(374)L mutants of CHS and STS showed no condensing activity with residual malonyl-CoA decarboxylase activity. These results suggested that the G(372)FGPG loop in CHS and STS contribute to a determination of the outcome during cyclization reactions by serving as a part of the active-site scaffold on which the stereochemistry of cyclization is performed. These observations provide the first biochemical indication that cyclization reactions are modulated by active-site geometry. The implications for the evolutionary relationship of these enzymes are also discussed. PMID:10926848

Suh, D Y; Fukuma, K; Kagami, J; Yamazaki, Y; Shibuya, M; Ebizuka, Y; Sankawa, U

2000-08-15

328

Tabletop imaging of structural evolutions in chemical reactions demonstrated for the acetylene cation  

NASA Astrophysics Data System (ADS)

The introduction of femto-chemistry has made it a primary goal to follow the nuclear and electronic evolution of a molecule in time and space as it undergoes a chemical reaction. Using Coulomb Explosion Imaging, we have shot the first high-resolution molecular movie of a to and fro isomerization process in the acetylene cation. So far, this kind of phenomenon could only be observed using vacuum ultraviolet light from a free-electron laser. Here we show that 266?nm ultrashort laser pulses are capable of initiating rich dynamics through multiphoton ionization. With our generally applicable tabletop approach that can be used for other small organic molecules, we have investigated two basic chemical reactions simultaneously: proton migration and C=C bond breaking, triggered by multiphoton ionization. The experimental results are in excellent agreement with the timescales and relaxation pathways predicted by new and quantitative ab initio trajectory simulations.

Ibrahim, Heide; Wales, Benji; Beaulieu, Samuel; Schmidt, Bruno E.; Thiré, Nicolas; Fowe, Emmanuel P.; Bisson, Éric; Hebeisen, Christoph T.; Wanie, Vincent; Giguére, Mathieu; Kieffer, Jean-Claude; Spanner, Michael; Bandrauk, André D.; Sanderson, Joseph; Schuurman, Michael S.; Légaré, François

2014-07-01

329

Tabletop imaging of structural evolutions in chemical reactions demonstrated for the acetylene cation.  

PubMed

The introduction of femto-chemistry has made it a primary goal to follow the nuclear and electronic evolution of a molecule in time and space as it undergoes a chemical reaction. Using Coulomb Explosion Imaging, we have shot the first high-resolution molecular movie of a to and fro isomerization process in the acetylene cation. So far, this kind of phenomenon could only be observed using vacuum ultraviolet light from a free-electron laser. Here we show that 266 nm ultrashort laser pulses are capable of initiating rich dynamics through multiphoton ionization. With our generally applicable tabletop approach that can be used for other small organic molecules, we have investigated two basic chemical reactions simultaneously: proton migration and C=C bond breaking, triggered by multiphoton ionization. The experimental results are in excellent agreement with the timescales and relaxation pathways predicted by new and quantitative ab initio trajectory simulations. PMID:25034613

Ibrahim, Heide; Wales, Benji; Beaulieu, Samuel; Schmidt, Bruno E; Thiré, Nicolas; Fowe, Emmanuel P; Bisson, Éric; Hebeisen, Christoph T; Wanie, Vincent; Giguére, Mathieu; Kieffer, Jean-Claude; Spanner, Michael; Bandrauk, André D; Sanderson, Joseph; Schuurman, Michael S; Légaré, François

2014-01-01

330

Differentiation and replication of spots in a reaction-diffusion system with many chemicals  

NASA Astrophysics Data System (ADS)

The replication and differentiation of spots in reaction-diffusion equations are studied by extending the Gray-Scott model with self-replicating spots to include many degrees of freedom needed to model systems with many chemicals. By examining many possible reaction networks, the behavior of this model is categorized into three types: replication of homogeneous fixed spots, replication of oscillatory spots, and differentiation from "multipotent spots" . These multipotent spots either replicate or differentiate into other types of spots with different fixed-point dynamics, and, as a result, an inhomogeneous pattern of spots is formed. This differentiation process of spots is analyzed in terms of the loss of chemical diversity and decrease of the local Kolmogorov-Sinai entropy. The relevance of the results to developmental cell biology and stem cells is also discussed.

Takagi, H.; Kaneko, K.

2001-10-01

331

Quantum adiabatic theorem for chemical reactions and systems with time-dependent orthogonalization  

E-print Network

A general quantum adiabatic theorem with and without the time-dependent orthogonalization is proven, which can be applied to understand the origin of activation energies in chemical reactions. Further proofs are also developed for the oscillating Schwinger Hamiltonian to establish the relationship between the internal (due to time-dependent eigenfunctions) and external (due to time-dependent Hamiltonian) time scales. We prove that this relationship needs to be taken as an independent quantum adiabatic approximation criterion. We give four examples, including logical expositions based on the spin-1/2 two-level system to address the gapped and gapless (due to energy level crossings) systems, as well as to understand how does this theorem allows one to study dynamical systems such as chemical reactions.

Andrew Das Arulsamy

2010-06-30

332

Chemical TOPAZ: Modifications to the heat transfer code TOPAZ: The addition of chemical reaction kinetics and chemical mixtures  

SciTech Connect

This is a report describing the modifications which have been made to the heat flow code TOPAZ to allow the inclusion of thermally controlled chemical kinetics. This report is broken into parts. The first part is an introduction to the general assumptions and theoretical underpinning that were used to develop the model. The second section describes the changes that have been implemented into the code. The third section is the users manual for the input for the code. The fourth section is a compilation of hints, common errors, and things to be aware of while you are getting started. The fifth section gives a sample problem using the new code. This manual addenda is written with the presumption that most readers are not fluent with chemical concepts. Therefore, we shall in this section endeavor to describe the requirements that must be met before chemistry can occur and how we have modeled the chemistry in the code.

Nichols, A.L. III.

1990-06-07

333

Coupling of Hydrologic Transport and Chemical Reactions in a Stream Affected by Acid Mine Drainage  

Microsoft Academic Search

~~~~~ ~ Experiments in St. Kevin Gulch, an acid mine drainage stream, examined the coupling of hydrologic transport to chemical reactions affecting metal concentrations. Injec- tion of LiCl as a conservative tracer was used to determine discharge and residence time along a 1497-m reach. Transport of metals downstream from inflows of acidic, metal-rich water was evaluated based on synoptic samples

Briant A. Kimball; Robert E. Broshears; Kenneth E. Bencala; Diane M. McKnight

1994-01-01

334

Apparatus for studies of high-temperature chemical reactions in single particle systems.  

PubMed

We report a compact microgravity flight apparatus for characterization of high-temperature chemical reactions in single particle systems. The apparatus employs an infrared CO(2) laser to ignite 1-5 mm samples while video images, thermocouple measurements, laser on/off status, and XYZ accelerometer signals are synchronously recorded. Different operating modes permit preignition quenching, ignition, and combustion experiments to be performed. The apparatus was successfully utilized during microgravity experiments on board NASA research aircraft. PMID:17764350

Andrzejak, Timothy A; Shafirovich, Evgeny; Taylor, David G; Varma, Arvind

2007-08-01

335

Apparatus for studies of high-temperature chemical reactions in single particle systems  

NASA Astrophysics Data System (ADS)

We report a compact microgravity flight apparatus for characterization of high-temperature chemical reactions in single particle systems. The apparatus employs an infrared CO2 laser to ignite 1-5mm samples while video images, thermocouple measurements, laser on/off status, and XYZ accelerometer signals are synchronously recorded. Different operating modes permit preignition quenching, ignition, and combustion experiments to be performed. The apparatus was successfully utilized during microgravity experiments on board NASA research aircraft.

Andrzejak, Timothy A.; Shafirovich, Evgeny; Taylor, David G.; Varma, Arvind

2007-08-01

336

Role of graphene on the surface chemical reactions of BiPO4-rGO with low OH-related defects.  

PubMed

Graphene has been widely introduced into photocatalysis to enhance photocatalytic performance due to its unique physical and chemical properties. However, the effect of graphene on the surface chemical reactions of photocatalysis has not been clearly researched, which is important for photocatalysis because photocatalytic reactions ultimately occur on the catalyst surface. Herein, a two-step solution-phase reaction has been designed to synthesize quasi-core-shell structured BiPO4-rGO cuboids and the role of graphene on the surface chemical reactions was investigated in detail. It was found that the introduced graphene modified the process and the mechanism of the surface chemical reactions. The change mainly originates from the interaction between graphene and the adsorbed O2 molecule. Due to the electron transfer from graphene to adsorbed O2, graphene could tune the interfacial charge transport and efficiently activate molecular oxygen to form O2?(-) anions as the major oxidation species instead of ?OH. In addition, the two-step synthesis approach could efficiently suppress the formation of OH-related defects in the lattice. As a result, the BiPO4-rGO composite exhibited superior photocatalytic activity to BiPO4 and P25, about 4.3 times that of BiPO4 and 6.9 times that of P25. PMID:24056863

Gao, Erping; Wang, Wenzhong

2013-11-21

337

The importance of evaluating the physicochemical and toxicological properties of a contaminant for remediating environments affected by chemical incidents.  

PubMed

In the event of a major chemical incident or accident, appropriate tools and technical guidance need to be available to ensure that a robust approach can be adopted for developing a remediation strategy. Remediation and restoration strategies implemented in the aftermath of a chemical incident are a particular concern for public health. As a result an innovative methodology has been developed to help design an effective recovery strategy in the aftermath of a chemical incident that has been developed; the UK Recovery Handbook for Chemical Incidents (UKRHCI). The handbook consists of a six-step decision framework and the use of decision trees specifically designed for three different environments: food production systems, inhabited areas and water environments. It also provides a compendium of evidence-based recovery options (techniques or methods for remediation) that should be selected in relation to their efficacy for removing contaminants from the environment. Selection of effective recovery options in this decision framework involves evaluating the physicochemical and toxicological properties of the chemical(s) involved. Thus, the chemical handbook includes a series of tables with relevant physicochemical and toxicological properties that should be assessed in function of the environment affected. It is essential that the physicochemical properties of a chemical are evaluated and interpreted correctly during the development of a remedial plan in the aftermath of a chemical incident to ensure an effective remedial response. This paper presents a general overview of the key physicochemical and toxicological properties of chemicals that should be evaluated when developing a recovery strategy. Information on how physicochemical properties have impacted on previous remedial responses reported in the literature is also discussed and a number of challenges for remediation are highlighted to include the need to develop novel approaches to remediate sites contaminated by mixtures of chemicals as well as methods for interpreting chemical reactions in different environmental matrices to include how climate change may affect the speciation and mobility of chemicals in the environment. PMID:24874001

Wyke, S; Peña-Fernández, A; Brooke, N; Duarte-Davidson, R

2014-11-01

338

On the role of chemical reactions in initiating ultraviolet laser ablation in poly(methyl methacrylate)  

SciTech Connect

The role of chemical reactions is investigated versus the thermal and mechanical processes occurring in a polymer substrate during irradiation by a laser pulse and subsequent ablation. Molecular dynamics simulations with an embedded Monte Carlo based reaction scheme were used to study ultraviolet ablation of poly(methyl methacrylate) at 157 nm. We discuss the onset of ablation, the mechanisms leading to ablation, and the role of stress relaxation of the polymer matrix during ablation. Laser induced heating and chemical decomposition of the polymer substrate are considered as ablation pathways. It is shown that heating the substrate can set off ablation via mechanical failure of the material only for very short laser pulses. For longer pulses, the mechanism of ejection is thermally driven limited by the critical number of bonds broken in the substrate. Alternatively, if the photon energy goes towards direct bond breaking, it initiates chemical reactions, polymer unzipping, and formation of gaseous products, leading to a nearly complete decomposition of the top layers of substrates. The ejection of small molecules has a hollowing out effect on the weakly connected substrates which can lead to lift-off of larger chunks. Excessive pressure buildup upon the creation of gaseous molecules does not lead to enhanced yield. The larger clusters are thermally ejected, and an entrainment of larger polymer fragments in gaseous molecules is not observed.

Prasad, Manish; Conforti, Patrick F.; Garrison, Barbara J. [Department of Chemistry, 104 Chemistry Building, The Pennsylvania State University, University Park, Pennsylvania 16802 (United States)

2007-05-15

339

General method and thermodynamic tables for computation of equilibrium composition and temperature of chemical reactions  

NASA Technical Reports Server (NTRS)

A rapidly convergent successive approximation process is described that simultaneously determines both composition and temperature resulting from a chemical reaction. This method is suitable for use with any set of reactants over the complete range of mixture ratios as long as the products of reaction are ideal gases. An approximate treatment of limited amounts of liquids and solids is also included. This method is particularly suited to problems having a large number of products of reaction and to problems that require determination of such properties as specific heat or velocity of sound of a dissociating mixture. The method presented is applicable to a wide variety of problems that include (1) combustion at constant pressure or volume; and (2) isentropic expansion to an assigned pressure, temperature, or Mach number. Tables of thermodynamic functions needed with this method are included for 42 substances for convenience in numerical computations.

Huff, Vearl N; Gordon, Sanford; Morrell, Virginia E

1951-01-01

340

Skin hypersensitivity reactions to transdermal therapeutic systems--still an important clinical problem.  

PubMed

Transdermal therapeutic systems (TTS) belong to the widely used methods of drug administration, which allow rate-controlled drug delivery and avoidance of first-pass metabolism in the liver Beside scopolamine, nitroglycerin (glyceryl trinitrate), nicotine, clonidine and fentanyl, also transdermal delivery of sex steroids for hormone replacement therapy and contraception is a well-known and popular method in daily clinical practice. It is estimated that approximately 20% of patients using transdermal estradiol may complain of adverse cutaneous side effects. Most of those reactions are mild or moderate, usually limited to the area of drug application. However, prolonged use may increase the chance of developing sensitization. The purpose of this review is to provide up-to date information on the spectrum of cutaneous reactions caused by TTS and the characteristics of potential contact allergens, including sex hormones. Proper management and prophylactic measures were also included. PMID:22384639

Jenerowicz, Dorota; Pola?ska, Adriana; Olek-Hrab, Karolina; Silny, Wojciech

2012-01-01

341

A DAG scheduling scheme on heterogeneous computing systems using tuple-based chemical reaction optimization.  

PubMed

A complex computing problem can be solved efficiently on a system with multiple computing nodes by dividing its implementation code into several parallel processing modules or tasks that can be formulated as directed acyclic graph (DAG) problems. The DAG jobs may be mapped to and scheduled on the computing nodes to minimize the total execution time. Searching an optimal DAG scheduling solution is considered to be NP-complete. This paper proposed a tuple molecular structure-based chemical reaction optimization (TMSCRO) method for DAG scheduling on heterogeneous computing systems, based on a very recently proposed metaheuristic method, chemical reaction optimization (CRO). Comparing with other CRO-based algorithms for DAG scheduling, the design of tuple reaction molecular structure and four elementary reaction operators of TMSCRO is more reasonable. TMSCRO also applies the concept of constrained critical paths (CCPs), constrained-critical-path directed acyclic graph (CCPDAG) and super molecule for accelerating convergence. In this paper, we have also conducted simulation experiments to verify the effectiveness and efficiency of TMSCRO upon a large set of randomly generated graphs and the graphs for real world problems. PMID:25143977

Jiang, Yuyi; Shao, Zhiqing; Guo, Yi

2014-01-01

342

Efficient exact and K-skip methods for stochastic simulation of coupled chemical reactions  

NASA Astrophysics Data System (ADS)

Gillespie's direct method (DM) [D. Gillespie, J. Chem. Phys. 81, 2340 (1977)] for exact stochastic simulation of chemical reaction systems has been widely adopted. It is easy to implement but requires large computation for relatively large systems. Recently, two more efficient methods, next reaction method (NRM) [M. A. Gibson and J. Bruck, J. Phys. Chem. A 105, 1876 (2000)] and optimized DM (ODM) [Y. Cao et al., J. Chem. Phys. 121, 4059 (2004)], have been developed to improve simulation speed. It has been demonstrated that the ODM is the state-of-the-art most efficient method for exact stochastic simulation of most practical reaction systems. In this paper, we first develop an exact stochastic simulation algorithm named ODMK that is more efficient than the ODM. We then develop an approximate method named K-skip method to further accelerate simulation. Using two chemical reaction systems, we demonstrate that our ODMK and K-skip method can save 20%-30% and 70%-80% simulation time, respectively, comparing to the ODM. We also show that our ODMK and K-skip method provide almost the same simulation accuracy as the ODM.

Cai, Xiaodong; Wen, Ji

2009-08-01

343

Novel duplex vapor: Electrochemical method for silicon solar cells. [chemical reactor for a silicon sodium reaction system  

NASA Technical Reports Server (NTRS)

The scaled up chemical reactor for a SiF4-Na reaction system is examined for increased reaction rate and production rate. The reaction system which now produces 5 kg batches of mixed Si and NaF is evaluated. The reactor design is described along with an analysis of the increased capacity of the Na chip feeder. The reactor procedure is discussed and Si coalescence in the reaction products is diagnosed.

Nanis, L.; Sanjurjo, A.; Sancier, K.

1979-01-01

344

Hypochlorous acid-mediated protein oxidation: how important are chloramine transfer reactions and protein tertiary structure?  

PubMed

Hypochlorous acid (HOCl) is a powerful oxidant generated from H2O2 and Cl- by the heme enzyme myeloperoxidase, which is released from activated leukocytes. HOCl possesses potent antibacterial properties, but excessive production can lead to host tissue damage that occurs in numerous human pathologies. As proteins and amino acids are highly abundant in vivo and react rapidly with HOCl, they are likely to be major targets for HOCl. In this study, two small globular proteins, lysozyme and insulin, have been oxidized with increasing excesses of HOCl to determine whether the pattern of HOCl-mediated amino acid consumption is consistent with reported kinetic data for isolated amino acids and model compounds. Identical experiments have been carried out with mixtures of N-acetyl amino acids (to prevent reaction at the alpha-amino groups) that mimic the protein composition to examine the role of protein structure on reactivity. The results indicate that tertiary structure facilitates secondary chlorine transfer reactions of chloramines formed on His and Lys side chains. In light of these data, second-order rate constants for reactions of Lys side chain and Gly chloramines with Trp side chains and disulfide bonds have been determined, together with those for further oxidation of Met sulfoxide by HOCl and His side chain chloramines. Computational kinetic models incorporating these additional rate constants closely predict the experimentally observed amino acid consumption. These studies provide insight into the roles of chloramine formation and three-dimensional structure on the reactions of HOCl with isolated proteins and demonstrate that kinetic models can predict the outcome of HOCl-mediated protein oxidation. PMID:17676767

Pattison, David I; Hawkins, Clare L; Davies, Michael J

2007-08-28

345

Extension of a Kinetic-Theory Approach for Computing Chemical-Reaction Rates to Reactions with Charged Particles  

NASA Technical Reports Server (NTRS)

Recently introduced molecular-level chemistry models that predict equilibrium and nonequilibrium reaction rates using only kinetic theory and fundamental molecular properties (i.e., no macroscopic reaction rate information) are extended to include reactions involving charged particles and electronic energy levels. The proposed extensions include ionization reactions, exothermic associative ionization reactions, endothermic and exothermic charge exchange reactions, and other exchange reactions involving ionized species. The extensions are shown to agree favorably with the measured Arrhenius rates for near-equilibrium conditions.

Liechty, Derek S.; Lewis, Mark J.

2010-01-01

346

Extension of a Kinetic-Theory Approach for Computing Chemical-Reaction Rates to Reactions with Charged Particles  

NASA Astrophysics Data System (ADS)

Recently introduced molecular-level chemistry models that predict equilibrium and nonequilibrium reaction rates using only kinetic theory and fundamental molecular properties (i.e., no macroscopic reaction rate information) are extended to include reactions involving charged particles and electronic energy levels. The proposed extensions include ionization reactions, exothermic associative ionization reactions, endothermic and exothermic charge exchange reactions, and other exchange reactions involving ionized species. The extensions are shown to agree favorably with the measured Arrhenius rates for near-equilibrium conditions.

Liechty, Derek S.; Lewis, Mark J.

2011-05-01

347

Accelerating the Computation of Detailed Chemical Reaction Kinetics for Simulating Combustion of Complex Fuels  

SciTech Connect

Combustion of hydrocarbon fuels has been a very challenging scientific and engineering problem due to the complexity of turbulent flows and hydrocarbon reaction kinetics. There is an urgent need to develop an efficient modeling capability to accurately predict the combustion of complex fuels. Detailed chemical kinetic models for the surrogates of fuels such as gasoline, diesel and JP-8 consist of thousands of chemical species and Arrhenius reaction steps. Oxygenated fuels such as bio-fuels and heavier hydrocarbons, such as from newer fossil fuel sources, are expected to have a much more complex chemistry requiring increasingly larger chemical kinetic models. Such models are beyond current computational capability, except for homogeneous or partially stirred reactor type calculations. The advent of highly parallel multi-core processors and graphical processing units (GPUs) promises a steep increase in computational performance in the coming years. This paper will present a software framework that translates the detailed chemical kinetic models to high- performance code targeted for GPU accelerators.

Grout, Ray W [ORNL

2012-01-01

348

Accelerating the Computation of Detailed Chemical Reaction Kinetics for Simulating Combustion of Complex Fuels  

SciTech Connect

Combustion of hydrocarbon fuels has been a very challenging scientific and engineering problem due to the complexity of turbulent flows and hydrocarbon reaction kinetics. There is an urgent need to develop an efficient modeling capability to accurately predict the combustion of complex fuels. Detailed chemical kinetic models for the surrogates of fuels such as gasoline, diesel and JP-8 consist of thousands of chemical species and Arrhenius reaction steps. Oxygenated fuels such as bio-fuels and heavier hydrocarbons, such as from newer fossil fuel sources, are expected to have a much more complex chemistry requiring increasingly larger chemical kinetic models. Such models are beyond current computational capability, except for homogeneous or partially stirred reactor type calculations. The advent of highly parallel multi-core processors and graphical processing units (GPUs) promises a steep increase in computational performance in the coming years. This paper will present a software framework that translates the detailed chemical kinetic models to high-performance code targeted for GPU accelerators.

Sankaran, R.; Grout, R.

2012-01-01

349

Simulation of gas absorption into string-of-beads liquid flow with chemical reaction  

NASA Astrophysics Data System (ADS)

This study is an attempt to investigate the chemical absorption of CO2 in aqueous monoethanolamine (MEA) solution in a wetted-wire column consisting of one wire. Computational fluid dynamics method along with volume of fluid model was employed for modeling of two-phase flow, mass transfer and chemical reaction inside the column. The modeling results were compared with available experimental data and very good agreement was achieved. The simulation results showed that the diameter and intervals of liquid beads increases by increasing the gas and liquid flow rates. The beads velocity increases by increasing the liquid flow rate and decreasing mass fraction of MEA in the liquid phase. Also, mass transfer resistance in the liquid phase reduces by formation of the beads. It was concluded that the developed model is capable to predict the effect of operating and physical parameters on the investigated chemical absorption process.

Hosseini, S. M.; Alizadeh, R.; Fatehifar, E.; Alizadehdakhel, A.

2014-10-01

350

Comprehensive study of the chemical reactions resulting from the decomposition of chloroform in alkaline aqueous solution  

NASA Astrophysics Data System (ADS)

Chloroform (CHCl3) is a volatile liquid, which has a rather slow rate of decomposition in ground water. It is a known carcinogen and one of the most common contaminants found at toxic waste sites. The dominant degradation process for chloroform in both the atmosphere and the groundwater is the reaction with the hydroxyl radical or hydroxide ion. This process triggers a sequence of reactions which ultimately yield carbon monoxide, hydrogen chloride, and formic acid. The rate of chloroform degradation is considerably larger in solution than that in the gas phase and it increases dramatically with increasing pH. However, only one of the viable reactions had been studied previously at a high level of theory in solution. It is of great interest to gain a deeper understanding of the decomposition reaction mechanism. Quantum mechanical methods are well suited for studying the mechanism of organic reactions. However, a full quantum mechanical treatment of the entire fluid system is not computationally feasible. In this work, combined quantum mechanical and molecular mechanical (QM/MM) methods are used for studying chemical reactions in condensed phases. In these calculations, the solute molecules are treated quantum mechanically (QM), whereas the solvent molecules are approximated by empirical (MM) potential energy functions. The use of quantum mechanics and statistical sampling simulation is necessary to determine the reaction free energy profile. In the present study, the ab initio Hartree-Fock theory along with the 3-21G basis set was used in the quantum mechanical calculations to elucidate the reaction pathways of chloroform decomposition, with a focus on basic reaction conditions. Statistical mechanical Monte Carlo approach was then applied in molecular mechanical simulations, employing the empirical TIP3P model for water. We employed state-of-the-art electronic structure methods to determine the gas-phase inter-nuclear potential energy profile for all the relevant reactions. Each gas-phase potential energy profile obtained at a high level of theory was used as a post-correction of the corresponding reaction free energy profile in aqueous solution. A detailed picture of the actual mechanism driving the decomposition pathway of chloroform has emerged from these simulations.

Estevez Mews, Jorge

351

Thermal decomposition reactions of HMX and RDX and their importance in predicting cookoff hazards  

SciTech Connect

Recent work on the decomposition of hexahydro-1,3,5-trinitro-s-triazine (RDX) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), utilizing simultaneous thermogravimetric modulated beam mass spectrometry (STMBMS), has shown that they undergo significant decomposition in both the solid and liquid phases. Previous studies have determined the mechanisms of several reaction pathways that control the decomposition of these materials. This paper presents a summary of this previous work and how the results can be applied to developing models to predict the response of energetic materials in cookoff situations.

Behrens, R. Jr. [Sandia National Labs., Livermore, CA (United States); Bulusu, S. [Army Armament Research, Development, and Engineering Center, Dover, NJ (United States)

1994-11-01

352

Modeling the effects of chemical exposure on avian seasonal productivity: Importance of differences in breeding strategies  

EPA Science Inventory

Agencies that regulate the use of chemicals are increasingly interested in understanding the magnitude of effects of those chemicals on wildlife populations. While laboratory toxicity tests provide insights into the types of effects caused by chemical exposure, they do not alway...

353

ABIOTIC REACTIONS MAY BE THE MOST IMPORTANT MECHANISM IN NATURAL ATTENUATION OF CHLORINATED SOLVENTS  

EPA Science Inventory

The EPA Technical Protocol for Evaluating Natural Attenuation of Chlorinated Solvents in Ground Water was developed with the assumption that natural biological reductive dechlorination was the only important mechanism for destruction of chlorinated solvents and their reduction ...

354

Electrochemically induced chemically reversible proton-coupled electron transfer reactions of riboflavin (vitamin B2).  

PubMed

The electrochemical behavior of the naturally occurring vitamin B(2), riboflavin (Fl(ox)), was examined in detail in dimethyl sulfoxide solutions using variable scan rate cyclic voltammetry (? = 0.1 - 20 V s(-1)) and has been found to undergo a series of proton-coupled electron transfer reactions. At a scan rate of 0.1 V s(-1), riboflavin is initially reduced by one electron to form the radical anion (Fl(rad)(•-)) at E(0)(f) = -1.22 V versus Fc/Fc(+) (E(0)(f) = formal reduction potential and Fc = ferrocene). Fl(rad)(•-) undergoes a homogeneous proton transfer reaction with the starting material (Fl(ox)) to produce Fl(rad)H(•) and Fl(ox)(-), which are both able to undergo further reduction at the electrode surface to form Fl(red)H(-) (E(0)(f) = -1.05 V vs Fc/Fc(+)) and Fl(rad)(•2-) (E(0)(f) = -1.62 V vs Fc/Fc(+)), respectively. At faster voltammetric scan rates, the homogeneous reaction between Fl(rad)(•-) and Fl(ox) begins to be outrun, which leads to the detection of a voltammetric peak at more negative potentials associated with the one-electron reduction of Fl(rad)(•-) to form Fl(red)(2-) (E(0)(f) = -1.98 V vs Fc/Fc(+)). The variable scan rate voltammetric data were modeled quantitatively using digital simulation techniques based on an interconnecting "scheme of squares" mechanism, which enabled the four formal potentials as well as the equilibrium and rate constants associated with four homogeneous reactions to be determined. Extended time-scale controlled potential electrolysis (t > hours) and spectroscopic (EPR and in situ UV-vis) experiments confirmed that the chemical reactions were completely chemically reversible. PMID:22390470

Tan, Serena L J; Webster, Richard D

2012-04-01

355

Modeling Cl2 formation from aqueous NaCl particles: Evidence for interfacial reactions and importance of Cl2 decomposition in alkaline solution  

NASA Astrophysics Data System (ADS)

A series of experiments have demonstrated that a significant yield of chlorine gas is produced when mixtures of ozone and sodium chloride particles above their deliquescence point are irradiated at 254 nm. In order to obtain expressions for future modeling studies, a comprehensive model is used to analyze the system and to determine its sensitivity. This work reexamines and expands previous studies [, 2000]. The enhanced model, described in detail herein, reaffirms that current known physical and chemical processes fail to reproduce the observed Cl2 formation in the experiments. A methodological analysis, proposed as a framework for similar studies, of the physicochemical system supports the accountability of an overall mechanism initiated by the formation of a relatively stable complex of the hydroxyl radical and chloride ions at the gas-liquid interface for the observed chlorine generation. Different potential fates of the OH•••Clsurface•- intermediate are discussed. A rate expression and kinetic parameters are presented for the overall reaction of the interfacial mechanism. In addition, sensitivity studies underscore the importance of accurately modeling chlorine decomposition processes in alkaline solution—in particular, the reactions of chlorine with hydroxide, carbonate, and basic hydrogen peroxide. Recommended aqueous-phase rate constants for these reactions are drawn from a literature evaluation illustrating the limited availability and lack of agreement of related kinetic data.

Knipping, Eladio M.; Dabdub, Donald

2002-09-01

356

The Importance of IgG Avidity and the Polymerase Chain Reaction in Treating Toxoplasmosis during Pregnancy: Current Knowledge  

PubMed Central

A brief report on the nature and epidemiology of T. gondii infection is firstly presented. The importance of the specific IgG avidity test and polymerase chain reaction (PCR) for toxoplasmosis is discussed, along with their significance and importance as auxiliary methods for determining the most likely time for the initial infection by this coccidian and for defining the therapeutic strategy. Lastly, practical comments are made in relation to the classical therapeutic regimens, with special attention to the indications for fetal treatment, when this is necessary. PMID:24191157

Bortoletti Filho, João; Carvalho, Natália da Silva; Helfer, Talita Micheletti; Nogueira Serni, Priscila de Oliveira; Nardozza, Luciano Marcondes Machado; Moron, Antonio Fernandes

2013-01-01

357

Phase transition between nanostructures of titanate and titanium dioxides via simple wet-chemical reactions.  

PubMed

Titanate nanofibers of various sizes and layered structure were prepared from inorganic titanium compounds by hydrothermal reactions. These fibers are different from "refractory" mineral substances because of their dimension, morphology, and significant large ratio of surface to volume, and, surprisingly, they are highly reactive. We found, for the first time, that phase transitions from the titanate nanostructures to TiO(2) polymorphs take place readily in simple wet-chemical processes at temperatures close to ambient temperature. In acidic aqueous dispersions, the fibers transform to anatase and rutile nanoparticles, respectively, but via different mechanisms. The titanate fibers prepared at lower hydrothermal temperatures transform to TiO(2) polymorphs at correspondingly lower temperatures because they are thinner, possess a larger surface area and more defects, and possess a less rigid crystal structure, resulting in lower stability. The transformations are reversible: in this case, the obtained TiO(2) nanocrystals reacted with concentrate NaOH solution, yielding hollow titanate nanotubes. Consequently, there are reversible transformation pathways for transitions between the titanates and the titanium dioxide polymorphs, via wet-chemical reactions at moderate temperatures. The significance of these findings arises because such transitions can be engineered to produce numerous delicate nanostructures under moderate conditions. To demonstrate the commercial application potential of these processes, we also report titanate and TiO(2) nanostructures synthesized directly from rutile minerals and industrial-grade rutiles by a new scheme of hydrometallurgical reactions. PMID:15869295

Zhu, H Y; Lan, Y; Gao, X P; Ringer, S P; Zheng, Z F; Song, D Y; Zhao, J C

2005-05-11

358

Fast stochastic simulation of biochemical reaction systems by alternative formulations of the chemical Langevin equation  

NASA Astrophysics Data System (ADS)

The Chemical Langevin Equation (CLE), which is a stochastic differential equation driven by a multidimensional Wiener process, acts as a bridge between the discrete stochastic simulation algorithm and the deterministic reaction rate equation when simulating (bio)chemical kinetics. The CLE model is valid in the regime where molecular populations are abundant enough to assume their concentrations change continuously, but stochastic fluctuations still play a major role. The contribution of this work is that we observe and explore that the CLE is not a single equation, but a parametric family of equations, all of which give the same finite-dimensional distribution of the variables. On the theoretical side, we prove that as many Wiener processes are sufficient to formulate the CLE as there are independent variables in the equation, which is just the rank of the stoichiometric matrix. On the practical side, we show that in the case where there are m1 pairs of reversible reactions and m2 irreversible reactions there is another, simple formulation of the CLE with only m1+m2 Wiener processes, whereas the standard approach uses 2m1+m2. We demonstrate that there are considerable computational savings when using this latter formulation. Such transformations of the CLE do not cause a loss of accuracy and are therefore distinct from model reduction techniques. We illustrate our findings by considering alternative formulations of the CLE for a human ether a-go-go related gene ion channel model and the Goldbeter-Koshland switch.

Mélykúti, Bence; Burrage, Kevin; Zygalakis, Konstantinos C.

2010-04-01

359

Screening effects in low energy nuclear reactions of importance to astrophysics  

Microsoft Academic Search

Recent experiments around the world., exemplified by those carried out at the LUNA (Laboratory for Underground Nuclear Astrophysics) collaboration, have shown that an anonymously high electron screening effect on nuclear fusion rate occurs during accelerator-driven low energy (< 10 kV) ion bombardment of solid targets. These effects become particularly important for E\\/Ue < 100 (where E = ion energy and

G. H. Miley; N. Luo; H. Hora; A. G. Lipson

2003-01-01

360

Thermal decomposition reactions of HMX and RDX and their importance in predicting cookoff hazards  

SciTech Connect

To develop robust models for predicting the response of munitions under abnormal conditions associated with cookoff, it is necessary to be able to accurately characterize the following: the time to ignition, the location of the ignition point within the munition, and the combustive behavior of the damaged energetic material after ignition. For, the response of the munition, as controlled by these parameters, will determine whether its response will be characterized by a relatively mild deflagration or whether it will be characterized by a more damaging detonation. Several of the underlying properties of the energetic materials used in munitions that must be understood in order to accurately characterize these parameters are the chemical and physical changes that occur in these energetic materials as they are heated. The chemical changes involve overcoming the forces that tend to stabilize these materials, such as binding within the crystal lattice or intermolecular hydrogen bonding, and their transformation to less stable forms, such as mixtures of gases with high energy content. The physical changes typically involve phase changes of the material. One significant phase change is the slow transformation of the energetic materials from the solid reactant to gas phase products. This transformation can lead initially to the formation of high pressure gas bubbles within the solid particles and ultimately to changes in the porosity and gas permeability of the energetic material formulation. The presence of these reactive gases within high pressure bubbles can lead to increased hot spot formation of the material if it is compressed. The increased porosity can lead to significant increases in the burn rates of these materials at high pressures.

Behrens, R. Jr. [Sandia National Labs., Livermore, CA (United States); Bulusu, S. [Army Research and Development Command, Dover, NJ (United States)

1994-05-01

361

A Coupled Dynamical Model of Redox Flow Battery Based on Chemical Reaction, Fluid Flow, and Electrical Circuit  

NASA Astrophysics Data System (ADS)

The redox (Reduction-Oxidation) flow battery is one of the most promising rechargeable batteries due to its ability to average loads and output of power sources. The transient characteristics are well known as the remarkable feature of the battery. Then it can also compensate for a sudden voltage drop. The dynamics are governed by the chemical reactions, fluid flow, and electrical circuit of its structure. This causes the difficulty of the analysis at transient state. This paper discusses the transient behavior of the redox flow battery based on chemical reactions. The concentration change of vanadium ions depends on the chemical reactions and the flow of electrolysis solution. The chemical reaction rate is restricted by the attached external electric circuit. In this paper, a model of the transient behavior is introduced. The validity of the derived model is examined based on experiments for a tested micro-redox flow battery system.

Li, Minghua; Hikihara, Takashi

362

FORMATION OF POLYCYCLIC AROMATIC HYDROCARBONS AND THEIR GROWTH TO SOOT -A REVIEW OF CHEMICAL REACTION PATHWAYS. (R824970)  

EPA Science Inventory

The generation by combustion processes of airborne species of current health concern such as polycyclic aromatic hydrocarbons (PAH) and soot particles necessitates a detailed understanding of chemical reaction pathways responsible for their formation. The present review discus...

363

15 CFR 713.1 - Prohibition on exports and imports of Schedule 2 chemicals to and from States not Party to the CWC.  

Code of Federal Regulations, 2011 CFR

...on exports and imports of Schedule 2 chemicals to and from States not Party to the...SECURITY, DEPARTMENT OF COMMERCE CHEMICAL WEAPONS CONVENTION REGULATIONS ACTIVITIES INVOLVING SCHEDULE 2 CHEMICALS § 713.1 Prohibition on...

2011-01-01

364

15 CFR 713.1 - Prohibition on exports and imports of Schedule 2 chemicals to and from States not Party to the CWC.  

...on exports and imports of Schedule 2 chemicals to and from States not Party to the...SECURITY, DEPARTMENT OF COMMERCE CHEMICAL WEAPONS CONVENTION REGULATIONS ACTIVITIES INVOLVING SCHEDULE 2 CHEMICALS § 713.1 Prohibition on...

2014-01-01

365

15 CFR 713.1 - Prohibition on exports and imports of Schedule 2 chemicals to and from States not Party to the CWC.  

Code of Federal Regulations, 2010 CFR

...on exports and imports of Schedule 2 chemicals to and from States not Party to the...SECURITY, DEPARTMENT OF COMMERCE CHEMICAL WEAPONS CONVENTION REGULATIONS ACTIVITIES INVOLVING SCHEDULE 2 CHEMICALS § 713.1 Prohibition on...

2010-01-01

366

15 CFR 713.1 - Prohibition on exports and imports of Schedule 2 chemicals to and from States not Party to the CWC.  

Code of Federal Regulations, 2013 CFR

...on exports and imports of Schedule 2 chemicals to and from States not Party to the...SECURITY, DEPARTMENT OF COMMERCE CHEMICAL WEAPONS CONVENTION REGULATIONS ACTIVITIES INVOLVING SCHEDULE 2 CHEMICALS § 713.1 Prohibition on...

2013-01-01

367

15 CFR 713.1 - Prohibition on exports and imports of Schedule 2 chemicals to and from States not Party to the CWC.  

Code of Federal Regulations, 2012 CFR

...on exports and imports of Schedule 2 chemicals to and from States not Party to the...SECURITY, DEPARTMENT OF COMMERCE CHEMICAL WEAPONS CONVENTION REGULATIONS ACTIVITIES INVOLVING SCHEDULE 2 CHEMICALS § 713.1 Prohibition on...

2012-01-01

368

A constrained reduced-dimensionality search algorithm to follow chemical reactions on potential energy surfaces  

NASA Astrophysics Data System (ADS)

A constrained reduced-dimensionality algorithm can be used to efficiently locate transition states and products in reactions involving conformational changes. The search path (SP) is constructed stepwise from linear combinations of a small set of manually chosen internal coordinates, namely the predictors. The majority of the internal coordinates, the correctors, are optimized at every step of the SP to minimize the total energy of the system so that the path becomes a minimum energy path connecting products and transition states with the reactants. Problems arise when the set of predictors needs to include weak coordinates, for example, dihedral angles, as well as strong ones such as bond distances. Two principal constraining methods for the weak coordinates are proposed to mend this situation: static and dynamic constraints. Dynamic constraints are automatically activated and revoked depending on the state of the weak coordinates among the predictors, while static ones require preset control factors and act permanently. All these methods enable the successful application (4 reactions are presented involving cyclohexane, alanine dipeptide, trimethylsulfonium chloride, and azafulvene) of the reduced dimensionality method to reactions where the reaction path covers large conformational changes in addition to the formation/breaking of chemical bonds. Dynamic constraints are found to be the most efficient method as they require neither additional information about the geometry of the transition state nor fine tuning of control parameters.

Lankau, Timm; Yu, Chin-Hui

2013-06-01

369

A constrained reduced-dimensionality search algorithm to follow chemical reactions on potential energy surfaces.  

PubMed

A constrained reduced-dimensionality algorithm can be used to efficiently locate transition states and products in reactions involving conformational changes. The search path (SP) is constructed stepwise from linear combinations of a small set of manually chosen internal coordinates, namely the predictors. The majority of the internal coordinates, the correctors, are optimized at every step of the SP to minimize the total energy of the system so that the path becomes a minimum energy path connecting products and transition states with the reactants. Problems arise when the set of predictors needs to include weak coordinates, for example, dihedral angles, as well as strong ones such as bond distances. Two principal constraining methods for the weak coordinates are proposed to mend this situation: static and dynamic constraints. Dynamic constraints are automatically activated and revoked depending on the state of the weak coordinates among the predictors, while static ones require preset control factors and act permanently. All these methods enable the successful application (4 reactions are presented involving cyclohexane, alanine dipeptide, trimethylsulfonium chloride, and azafulvene) of the reduced dimensionality method to reactions where the reaction path covers large conformational changes in addition to the formation/breaking of chemical bonds. Dynamic constraints are found to be the most efficient method as they require neither additional information about the geometry of the transition state nor fine tuning of control parameters. PMID:23758353

Lankau, Timm; Yu, Chin-Hui

2013-06-01

370

A simple model for product rovibrational distributions in elementary chemical reactions  

NASA Astrophysics Data System (ADS)

We explore the application of a simple model of collisional processes, developed initially for inelastic collisions, to the analysis of product rovibrational states in elementary chemical reactions. The model depicts collisional transfer as a process of momentum exchange (predominantly linear-to-angular momentum) and is modified to take account of change in center-of-mass and enthalpy change that accompany reaction. The kinematics of center-of-mass shift derived by Elsum and Gordon [J. Chem. Phys. 76, 3009 (1982)] lead to two limiting cases based on the parameter ?. The kinematic extremes alternatively may be specified in terms of the molecular torque arm about which interconversion of linear and angular momentum is effected. This torque arm length approximates to the product bond length when ??0 and the reactant bond length when ??90°. Our approach shares elements in common with the classical kinematic model of Elsum and Gordon but is somewhat simpler and more transparent. The method is shown to give accurate peak values of v, j states of the products of a wide range of elementary reactions for which experimental data is available. Monte Carlo trajectory calculations based on the physical principles described here give excellent fits to experimental v, j distributions in F+I2?IF+I, H+D2?HD+D, and Cl+H2?HCl+H using input data consisting of atomic radii, atomic masses, velocities, and reaction enthalpies.

Truhins, Kaspars; Marsh, Richard; McCaffery, Anthony J.; Whiteley, Thomas W. J.

2000-03-01

371

Photoexcited chemical wave in the ruthenium-catalyzed Belousov-Zhabotinsky reaction.  

PubMed

The excitation of the photosensitive Belousov-Zhabotinsky (BZ) reaction induced by light stimulation was systematically investigated. A stepwise increase in the light intensity induced the excitation, whereas a stepwise decrease did not induce the excitation. The threshold values for the excitation were found to be a function of the initial and final light intensities, time variation in light intensity, and the concentration of NaBrO(3). The experimental results were qualitatively reproduced by a theoretical calculation based on a three-variable Oregonator model modified for the photosensitive BZ reaction. These results suggest that although the steady light irradiation is known to inhibit oscillation and chemical waves in the BZ system under almost all conditions, the stepwise increase in the light irradiation leads to the rapid production of an activator, resulting in the photoexcitation. PMID:21563834

Nakata, Satoshi; Matsushita, Mariko; Sato, Taisuke; Suematsu, Nobuhiko J; Kitahata, Hiroyuki; Amemiya, Takashi; Mori, Yoshihito

2011-07-01

372

Generation of cavitation luminescence by laser-induced exothermic chemical reaction  

NASA Astrophysics Data System (ADS)

Absorption of high power laser radiation by aqueous carbon suspensions is known to result in the formation of highly compressed bubbles of hydrogen and carbon monoxide through the endothermic carbon-steam reaction. The bubbles expand rapidly, overreaching their equilibrium diameter, and then collapse tens to hundreds of microseconds after formation to give a flash of radiation. Here we report on the effects of laser-initiated exothermic chemical reaction on cavitation luminescence. Experiments with hydrogen peroxide added to colloidal carbon suspensions show that both the time of the light flash following the laser pulse and the intensity of luminescence increase with hydrogen peroxide concentration, indicating that large, highly energetic gas bubbles are produced. Additional experiments with colloidal carbon suspensions show the effects of high pressure on the luminescent intensity and its time of appearance following firing of the laser.

Jung Park, Han; Diebold, Gerald J.

2013-08-01

373

Using magnetic levitation to distinguish atomic-level differences in chemical composition of polymers, and to monitor chemical reactions on solid supports.  

PubMed

This communication describes a density-based method that uses magnetic levitation for monitoring solid-supported reactions and for distinguishing differences in chemical composition of polymers. The method is simple, rapid, and inexpensive and is similar to thin-layer chromatography (TLC; for solution-phase chemistry) in its potential for monitoring reactions in solid-phase chemistry. The technique involves levitating a sample of beads (taken from a reaction mixture) in a cuvette containing a paramagnetic solution (e.g., GdCl(3) dissolved in H(2)O) positioned between two NdFeB magnets. The vertical position at which the beads levitate corresponds to the density of the beads and correlates with the progress of a chemical reaction on a solid support. The method is particularly useful for monitoring the kinetics of reactions occurring on polymer beads. PMID:19063630

Mirica, Katherine A; Phillips, Scott T; Shevkoplyas, Sergey S; Whitesides, George M

2008-12-31

374

A numerical modelling of gas exchange mechanisms between air and turbulent water with an aquarium chemical reaction  

NASA Astrophysics Data System (ADS)

This paper proposes a new numerical modelling to examine environmental chemodynamics of a gaseous material exchanged between the air and turbulent water phases across a gas-liquid interface, followed by an aquarium chemical reaction. This study uses an extended concept of a two-compartment model, and assumes two physicochemical substeps to approximate the gas exchange processes. The first substep is the gas-liquid equilibrium between the air and water phases, A(g)?A(aq), with Henry's law constant H. The second is a first-order irreversible chemical reaction in turbulent water, A(aq)+H2O?B(aq)+H+ with a chemical reaction rate ?A. A direct numerical simulation (DNS) technique has been employed to obtain details of the gas exchange mechanisms and the chemical reaction in the water compartment, while zero velocity and uniform concentration of A is considered in the air compartment. The study uses the different Schmidt numbers between 1 and 8, and six nondimensional chemical reaction rates between 10(?0) to 101 at a fixed Reynolds number. It focuses on the effects of the Schmidt number and the chemical reaction rate on fundamental mechanisms of the gas exchange processes across the interface.

Nagaosa, Ryuichi S.

2014-01-01

375

Reprint of: A numerical modelling of gas exchange mechanisms between air and turbulent water with an aquarium chemical reaction  

NASA Astrophysics Data System (ADS)

This paper proposes a new numerical modelling to examine environmental chemodynamics of a gaseous material exchanged between the air and turbulent water phases across a gas-liquid interface, followed by an aquarium chemical reaction. This study uses an extended concept of a two-compartment model, and assumes two physicochemical substeps to approximate the gas exchange processes. The first substep is the gas-liquid equilibrium between the air and water phases, A(g)?A(aq), with Henry's law constant H. The second is a first-order irreversible chemical reaction in turbulent water, A(aq)+H2O?B(aq)+H+ with a chemical reaction rate ?A. A direct numerical simulation (DNS) technique has been employed to obtain details of the gas exchange mechanisms and the chemical reaction in the water compartment, while zero velocity and uniform concentration of A is considered in the air compartment. The study uses the different Schmidt numbers between 1 and 8, and six nondimensional chemical reaction rates between 10(?0) to 101 at a fixed Reynolds number. It focuses on the effects of the Schmidt number and the chemical reaction rate on fundamental mechanisms of the gas exchange processes across the interface.

Nagaosa, Ryuichi S.

2014-08-01

376

Astrophysically Important Reaction Rates For Novae And X-ray Bursts From Proton Breakup At Intermediate Energies  

SciTech Connect

We discuss the use of one-nucleon removal reactions of loosely bound nuclei at intermediate energies as an indirect method in nuclear astrophysics. The breakup reactions are proved to be good spectroscopic tools and can be used to study a large number of loosely bound proton- or neutron-rich nuclei over a wide range of beam energies. As peripheral processes, they can be used to extract asymptotic normalization coefficients (ANCs) from which non-resonant capture reaction rates of astrophysical interest can be calculated parameter free. In this talk, we present results of a proton-breakup experiment carried out at GANIL (France) with a cocktail beam centered around {sup 23}Al at 50 MeV/nucleon. Momentum distributions of the breakup fragments, inclusive and in coincidence with gamma rays detected by EXOGAM Germanium clover array, were measured in the focal plan of SPEG energy-loss spectrometer. We present in particular the investigations of reaction rates for {sup 22}Mg(p,{gamma}){sup 23}Al and {sup 23}Al(p,{gamma}){sup 24}Si important for novae and X-ray bursts, respectively.

Banu, A.; Trache, L. [Cyclotron Institute, Texas A and M University, College Station, Texas 77843-3366 (United States); National Institute of Physics and Nuclear Engineering, 'Horia Hulubei' (IFIN-HH), R-077125 Magurele-Bucharest (Romania); Carstoiu, F.; Negoita, F.; Rotaru, F. [National Institute of Physics and Nuclear Engineering, 'Horia Hulubei' (IFIN-HH), R-077125 Magurele-Bucharest (Romania); Orr, N. A.; Achouri, N. L.; Laurent, B. [Laboratoire de Physique Corpusculaire, IN2P3-CNRS, ISMRA et Universite, F-14050 Caen (France); Bonaccorso, A. [Instituto Nazionale di Fisica Nucleare, Sez. Di Pisa, I-56127 Pisa (Italy); Catford, W. N.; Patterson, N.; Thomas, J. S. [Department of Physics, University of Surrey, Guildford GU2 5XH (United Kingdom); Chartier, M.; Fernandez-Dominguez, B.; Paschalis, S.; Pietras, B. [Oliver Lodge Laboratory, University of Liverpool, Liverpool L69 7ZE (United Kingdom); Freer, M. [School of Physics and Astronomy, University of Birmingham, Birmingham B15 2TT (United Kingdom); Gaudefroy, L.; Roussel-Chomaz, P. [Grand Accelerateur d'Ions Lourds, BP 55027, 14076 Caen Cedex 5 (France); Horoi, M. [Department of Physics, Central Michigan University, Mount Pleasant, Michigan 48859 (United States)

2010-11-24

377

Steady State Detection of Chemical Reaction Networks Using a Simplified Analytical Method  

PubMed Central

Chemical reaction networks (CRNs) are susceptible to mathematical modelling. The dynamic behavior of CRNs can be investigated by solving the polynomial equations derived from its structure. However, simple CRN give rise to non-linear polynomials that are difficult to resolve. Here we propose a procedure to locate the steady states of CRNs from a formula derived through algebraic geometry methods. We have applied this procedure to define the steady states of a classic CRN that exhibits instability, and to a model of programmed cell death. PMID:20532219

Martínez-Forero, Ivan; Peláez-López, Antonio; Villoslada, Pablo

2010-01-01

378

Heat and mass transfer in unsteady rotating fluid flow with binary chemical reaction and activation energy.  

PubMed

In this study, the Spectral Relaxation Method (SRM) is used to solve the coupled highly nonlinear system of partial differential equations due to an unsteady flow over a stretching surface in an incompressible rotating viscous fluid in presence of binary chemical reaction and Arrhenius activation energy. The velocity, temperature and concentration distributions as well as the skin-friction, heat and mass transfer coefficients have been obtained and discussed for various physical parametric values. The numerical results obtained by (SRM) are then presented graphically and discussed to highlight the physical implications of the simulations. PMID:25250830

Awad, Faiz G; Motsa, Sandile; Khumalo, Melusi

2014-01-01

379

A Gas-Kinetic Scheme for Multimaterial Flows and Its Application in Chemical Reaction  

NASA Technical Reports Server (NTRS)

This paper concerns the extension of the multicomponent gas-kinetic BGK-type scheme to multidimensional chemical reactive flow calculations. In the kinetic model, each component satisfies its individual gas-kinetic BGK equation and the equilibrium states of both components are coupled in space and time due to the momentum and energy exchange in the course of particle collisions. At the same time, according to the chemical reaction rule one component can be changed into another component with the release of energy, where the reactant and product could have different gamma. Many numerical test cases are included in this paper, which show the robustness and accuracy of kinetic approach in the description of multicomponent reactive flows.

Lian, Yongsheng; Xu, Kun

1999-01-01

380

Tabulation of thermodynamic data for chemical reactions involving 58 elements common to radioactive waste package systems  

SciTech Connect

The rate of release and migration of radionuclides from a nuclear waste repository to the biosphere is dependent on chemical interactions between groundwater, the geologic host rock, and the radioactive waste package. For the purpose of this report, the waste package includes the wasteform, canister, overpack, and repository backfill. Chemical processes of interest include sorption (ion exchange), dissolution, complexation, and precipitation. Thermochemical data for complexation and precipitation calculations for 58 elements common to the radioactive waste package are presented. Standard free energies of formation of free ions, complexes, and solids are listed. Common logarithms of equilibrium constants (log K's) for speciation and precipitation reactions are listed. Unless noted otherwise, all data are for 298.15/sup 0/K and one atmosphere.

Benson, L.V.; Teague, L.S.

1980-08-01

381

Oxygen reduction reaction over silver particles with various morphologies and surface chemical states  

NASA Astrophysics Data System (ADS)

The oxygen reduction reaction (ORR) in an alkaline solution was carried out using Ag powders having various particle morphologies and surface chemical states (Size: ca. 40-110 nm in crystalline size. Shape: spherical, worm like, and angular. Surface: smooth with easily reduced AgOx, defective with AgOx, and Ag2CO3 surface layer). The various Ag powders were well characterized by X-ray diffraction, X-ray photoelectron spectroscopy, N2 adsorption, scanning electron microscopy, Raman spectroscopy, cyclic voltammetry, and stripping voltammetry of underpotential-deposited lead. Defective and oxidized surfaces enhanced the Ag active surface area during the ORR. The ORR activity was affected by the morphology and surface chemical state: Ag particles with defective and angular surfaces showed smaller electron exchange number between three and four but showed higher specific activity compared to Ag particles with smooth surfaces.

Ohyama, Junya; Okata, Yui; Watabe, Noriyuki; Katagiri, Makoto; Nakamura, Ayaka; Arikawa, Hidekazu; Shimizu, Ken-ichi; Takeguchi, Tatsuya; Ueda, Wataru; Satsuma, Atsushi

2014-01-01

382

Plasma-Assisted Reaction Chemical Ionization for Elemental Mass Spectrometry of Organohalogens  

NASA Astrophysics Data System (ADS)

We present plasma-assisted reaction chemical ionization (PARCI) for elemental analysis of halogens in organic compounds. Organohalogens are broken down to simple halogen-containing molecules (e.g., HBr) in a helium microwave-induced plasma followed by negative mode chemical ionization (CI) in the afterglow region. The reagent ions for CI originate from penning ionization of gases (e.g., N2) introduced into the afterglow region. The performance of PARCI-mass spectrometry (MS) is evaluated using flow injection analyses of organobromines, demonstrating 5-8 times better sensitivities compared with inductively coupled plasma MS. We show that compound-dependent sensitivities in PARCI-MS mainly arise from sample introduction biases.

Wang, Haopeng; Lin, Ninghang; Kahen, Kaveh; Badiei, Hamid; Jorabchi, Kaveh

2014-04-01

383

Chemical treatment of membranes of a polymer blend: Mechanism of the reaction of hypochlorite with poly(vinyl pyrrolidone)  

Microsoft Academic Search

Sodium hypochlorite solutions are used to treat membranes prepared from a polymeric blend containing poly(vinyl pyrrolidone) (PVP) to increase their water permeability. Sodium hypochlorite affects the membrane material in such a way that PVP is selectively removed from the membrane matrix. The mechanism of the reaction between hypochlorite and PVP is investigated by several chemical analysis techniques of the reaction

I. M. Wienk; E. E. B. Meuleman; Z. Borneman; Th. van den Boomgaard; C. A. Smolders

1995-01-01

384

Heterogeneous Reduction of PuO2 with Fe(II): Importance of the Fe(III) Reaction Product  

SciTech Connect

Abstract Heterogeneous reduction of actinides in higher and more soluble oxidation states to lower more insoluble oxidation states by reductants such as Fe(II) has been the subject of intensive study for more than two decades. However, Fe(II)-induced reduction of sparingly soluble Pu(IV) to the more soluble lower oxidation state Pu(III) has been much less studied even though such reactions can potentially increase the mobility of Pu in the subsurface. Thermodynamic calculations are presented that show how differences in the free energy of various possible solid-phase Fe(III) reaction products can greatly influence aqueous Pu(III) concentrations resulting from reduction of PuO2(am) by Fe(II). We present the first experimental evidence that reduction of PuO2(am) to Pu(III) by Fe(II) was enhanced when the Fe(III) mineral goethite was spiked into the reaction. The effect of goethite on reduction of Pu(IV) was demonstrated by measuring the time-dependence of total aqueous Pu concentration, its oxidation state, and system pe/pH. We also re-evaluated established protocols for determining Pu(III) [(Pu(III) + Pu(IV)) - Pu(IV)] by using thenoyltrifluoroacetone (TTA) in toluene extractions; the study showed that it is important to eliminate dissolved oxygen from the TTA solutions for accurate determinations. More broadly, this study highlights the importance of the Fe(III) reaction product in actinide reduction rate and extent by Fe(II).

Felmy, Andrew R.; Moore, Dean A.; Rosso, Kevin M.; Qafoku, Odeta; Rai, Dhanpat; Buck, Edgar C.; Ilton, Eugene S.

2011-05-01

385

Probabilistic Health Risk Assessment of Chemical Mixtures: Importance of Travel Times and Connectivity  

NASA Astrophysics Data System (ADS)

Subsurface contamination cases giving rise to groundwater pollutions are extensively found in all industrialized countries. Under this pressure, risk assessment methods play an important role in population protection by (1) quantifying the potential impact on human health of an aquifer contamination and (2) helping and driving decisions of groundwater-resource managers. Many reactive components such as chlorinated solvents or nitrates potentially experience attenuation processes under common geochemical conditions. This represents an attractive and extensively used remediation solution but leads often to the production of by-products before to reach a harmless chemical form. This renders mixtures of contaminants a common issue for groundwater resources managers. In this case, the threat posed by these contaminants to human health at a given sensitive location greatly depends on the competition between reactive and advective-dispersive characteristic times. However, hydraulic properties of the aquifer are known to be spatially variable, which can lead to the formation of preferential flow channels and fast contamination pathways. Therefore, the uncertainty on the spatial distribution of the aquifer properties controlling the plume travel time may then play a particular role in the human health risk assessment of chemical mixtures. We investigate here the risk related to a multispecies system in response to different degrees of heterogeneity of the hydraulic conductivity (K or Y =ln(K)). This work focuses on a Perchloroethylene (PCE) contamination problem followed by the sequential first-order production/biodegradation of its daughter species Trichloroethylene (TCE), Dichloroethylene (DCE) and Vinyl Chlorine (VC). For this specific case, VC is known to be a highly toxic contaminant. By performing numerical experiments, we evaluate transport through three-dimensional mildly (?Y 2=1.0) and highly (?Y 2=4.0) heterogeneous aquifers. Uncertainty on the hydraulic conductivity field is considered through a Monte Carlo scheme, and statistics of the total risk for human health (RT) related to the mixtures of the four carcinogenic plumes are evaluated. Results show two distinct spatiotemporal behavior of the RT estimation. Simulations in highly heterogeneous aquifers display a lower mean of RT close to the injection and higher further away. We explain this by the distinct ranges of travel times and connectivity metrics related to the two sets of aquifers. A high ?Y 2 trends to decrease the travel time (and increase the connectivity). Early travel times, associated to channeling effects, are intuitively perceived as an indicator for high risk. However, in our case, early travel times lead a limited production of highly toxic daughter species and a lower total risk. Our results reflect then the interplay between the characteristic reactive time for each component and the characteristic travel time of the plume since the production of VC depends on these factors.

Henri, Christopher V.; Fernàndez-Garcia, Daniel; de Barros, Felipe P. J.

2014-05-01

386

Time-resolved imaging of purely valence-electron dynamics during a chemical reaction  

NASA Astrophysics Data System (ADS)

Chemical reactions are manifestations of the dynamics of molecular valence electrons and their couplings to atomic motions. Emerging methods in attosecond science can probe purely electronic dynamics in atomic and molecular systems. By contrast, time-resolved structural-dynamics methods such as electron or X-ray diffraction and X-ray absorption yield complementary information about the atomic motions. Time-resolved methods that are directly sensitive to both valence-electron dynamics and atomic motions include photoelectron spectroscopy and high-harmonic generation: in both cases, this sensitivity derives from the ionization-matrix element. Here we demonstrate a time-resolved molecular-frame photoelectron-angular-distribution (TRMFPAD) method for imaging the purely valence-electron dynamics during a chemical reaction. Specifically, the TRMFPADs measured during the non-adiabatic photodissociation of carbon disulphide demonstrate how the purely electronic rearrangements of the valence electrons can be projected from inherently coupled electronic-vibrational dynamics. Combined with ongoing efforts in molecular frame alignment and orientation, TRMFPADs offer the promise of directly imaging valence-electron dynamics during molecular processes without involving the use of strong, highly perturbing laser fields.

Hockett, Paul; Bisgaard, Christer Z.; Clarkin, Owen J.; Stolow, Albert

2011-08-01

387

Effect of first-order chemical reaction on gravitational instability in a porous medium  

NASA Astrophysics Data System (ADS)

To understand the CO2 sequestration in the saline aquifer, the effect of a first-order chemical reaction on the onset of the buoyancy-driven instability in an isotropic reactive porous medium is analyzed theoretically. Under the linear stability theory, the stability equations are derived in the semi-infinite domain and they are solved with and without the quasi-steady-state approximation. We also considered the stability of the reactive system at a steady-state limit. The analysis for the steady-state case proposed that the onset of instability motion can occur during the transient period even if the system is stable at the steady state. Through the initial growth rate analysis the most unstable initial disturbance is determined, and it is found that initially the system is unconditionally stable regardless of the Damköhler number Da and the Darcy-Rayleigh number Ra . Based on the results of the initial growth rate analysis, the direct numerical simulation is also conducted by using the Fourier pseudospectral method. The present theoretical and numerical analyses suggest that the chemical reaction makes the system stable and no convective motion can be expected for Da/R a2 >2.5 ×10-3 .

Kim, Min Chan; Choi, Chang Kyun

2014-11-01

388

Molecular Switch Based on a Biologically Important Redox Reaction Ping Yan, Michael W. Holman, Paul Robustelli, Arindam Chowdhury, Fady I. Ishak, and  

E-print Network

Molecular Switch Based on a Biologically Important Redox Reaction Ping Yan, Michael W. Holman, Paul are now commercially available,30 switches based on reversible redox reactions are fewer and less well Building on our earlier report of a single-molecule probe,1 we show how biologically important redox

Chowdhury, Arindam

389

Influence of exothermic chemical reactions on laser-induced shock waves.  

PubMed

Differences in the excitation of non-energetic and energetic residues with a 900 mJ, 6 ns laser pulse (1064 nm) have been investigated. Emission from the laser-induced plasma of energetic materials (e.g. triaminotrinitrobenzene [TATB], cyclotrimethylene trinitramine [RDX], and hexanitrohexaazaisowurtzitane [CL-20]) is significantly reduced compared to non-energetic materials (e.g. sugar, melamine, and l-glutamine). Expansion of the resulting laser-induced shock wave into the air above the sample surface was imaged on a microsecond timescale with a high-speed camera recording multiple frames from each laser shot; the excitation of energetic materials produces larger heat-affected zones in the surrounding atmosphere (facilitating deflagration of particles ejected from the sample surface), results in the formation of additional shock fronts, and generates faster external shock front velocities (>750 m s(-1)) compared to non-energetic materials (550-600 m s(-1)). Non-explosive materials that undergo exothermic chemical reactions in air at high temperatures such as ammonium nitrate and magnesium sulfate produce shock velocities which exceed those of the inert materials but are less than those generated by the exothermic reactions of explosive materials (650-700 m s(-1)). The most powerful explosives produced the highest shock velocities. A comparison to several existing shock models demonstrated that no single model describes the shock propagation for both non-energetic and energetic materials. The influence of the exothermic chemical reactions initiated by the pulsed laser on the velocity of the laser-induced shock waves has thus been demonstrated for the first time. PMID:25182866

Gottfried, Jennifer L

2014-10-21

390

Transmission coefficients for chemical reactions with multiple states: role of quantum decoherence.  

PubMed

Transition-state theory (TST) is a widely accepted paradigm for rationalizing the kinetics of chemical reactions involving one potential energy surface (PES). Multiple PES reaction rate constants can also be estimated within semiclassical approaches provided the hopping probability between the quantum states is taken into account when determining the transmission coefficient. In the Marcus theory of electron transfer, this hopping probability was historically calculated with models such as Landau-Zener theory. Although the hopping probability is intimately related to the question of the transition from the fully quantum to the semiclassical description, this issue is not adequately handled in physicochemical models commonly in use. In particular, quantum nuclear effects such as decoherence or dephasing are not present in the rate constant expressions. Retaining the convenient semiclassical picture, we include these effects through the introduction of a phenomenological quantum decoherence function. A simple modification to the usual TST rate constant expression is proposed: in addition to the electronic coupling, a characteristic decoherence time ?(dec) now also appears as a key parameter of the rate constant. This new parameter captures the idea that molecular systems, although intrinsically obeying quantum mechanical laws, behave semiclassically after a finite but nonzero amount of time (?(dec)). This new degree of freedom allows a fresh look at the underlying physics of chemical reactions involving more than one quantum state. The ability of the proposed formula to describe the main physical lines of the phenomenon is confirmed by comparison with results obtained from density functional theory molecular dynamics simulations for a triplet to singlet transition within a copper dioxygen adduct relevant to the question of dioxygen activation by copper monooxygenases. PMID:21344903

de la Lande, Aurélien; ?ezá?, Jan; Lévy, Bernard; Sanders, Barry C; Salahub, Dennis R

2011-03-23

391

Feasibility Study of Venus Surface Cooling Using Chemical Reactions with the Atmosphere  

NASA Technical Reports Server (NTRS)

A literature search and theoretical analysis were conducted to investigate the feasibility of cooling a craft on Venus through chemical reformation of materials from the atmosphere. The core concept was to take carbon dioxide (CO2) from the Venus atmosphere and chemically reform it into simpler compounds such as carbon, oxygen, and carbon monoxide. This process is endothermic, taking energy from the surroundings to produce a cooling effect. A literature search was performed to document possible routes for achieving the desired reactions. Analyses indicated that on Venus, this concept could theoretically be used to produce cooling, but would not perform as well as a conventional heat pump. For environments other than Venus, the low theoretical performance limits general applicability of this concept, however this approach to cooling may be useful in niche applications. Analysis indicated that environments with particular atmospheric compositions and temperatures could allow a similar cooling system to operate with very good performance. This approach to cooling may also be useful where the products of reaction are also desirable, or for missions where design simplicity is valued. Conceptual designs for Venus cooling systems were developed using a modified concept, in which an expendable reactant supply would be used to promote more energetically favorable reactions with the ambient CO2, providing cooling for a more limited duration. This approach does not have the same performance issues, but the use of expendable supplies increases the mass requirements and limits the operating lifetime. This paper summarizes the findings of the literature search and corresponding analyses of the various cooling options.

Evans, Christopher

2013-01-01

392

Feasibility Study of Venus Surfuce Cooling Using Chemical Reactions with the Atmosphere  

NASA Technical Reports Server (NTRS)

A literature search and theoretical analysis were conducted to investigate the feasibility of cooling a craft on Venus through chemical reformation of materials from the atmosphere. The core concept was to take carbon dioxide (CO2) from the Venus atmosphere and chemically reform it into simpler compounds such as carbon, oxygen, and carbon monoxide. This process is endothermic, taking energy from the surroundings to produce a cooling effect. A literature search was performed to document possible routes for achieving the desired reactions. Analyses indicated that on Venus, this concept could theoretically be used to produce cooling, but would not perform as well as a conventional heat pump. For environments other than Venus, the low theoretical performance limits general applicability of this concept, however this approach to cooling may be useful in niche applications. Analysis indicated that environments with particular atmospheric compositions and temperatures could allow a similar cooling system to operate with very good performance. This approach to cooling may also be useful where the products of reaction are also desirable, or for missions where design simplicity is valued. Conceptual designs for Venus cooling systems were developed using a modified concept, in which an expendable reactant supply would be used to promote more energetically favorable reactions with the ambient CO2, providing cooling for a more limited duration. This approach does not have the same performance issues, but the use of expendable supplies increases the mass requirements and limits the operating lifetime. This paper summarizes the findings of the literature search and corresponding analyses of the various cooling options

Evans, Christopher

2013-01-01

393

Effect of the Gouy phase on the coherent phase control of chemical reactions  

NASA Astrophysics Data System (ADS)

We show how the spatial phase of a focused laser beam may be used as a tool for controlling the branching ratio of a chemical reaction. Guoy discovered [Acad. Sci., Paris, C. R. 110, 1250 (1890)] that when an electromagnetic wave passes through a focus its phase increases by ?. In a coherent control scheme involving the absorption of n photons of frequency ?m and m photons of frequency ?n, the overall phase shift produced by the Gouy phase is (n-m)?. At any given point in space, this phase shift is identical for all reaction products. Nevertheless, if the yields for different reaction channels have different intensity dependencies, the Gouy phase produces a net phase lag between the products that varies with the axial coordinate of the laser focus. We obtain here analytical and numerical values of this phase as the laser focus is scanned across the diameter of the molecular beam, taking into account the Rayleigh range and astigmatism of the laser beam and saturation of the transition. We also show that the modulation depth of the interference pattern may be increased by optimizing the relative intensities of the two fields.

Gordon, Robert J.; Barge, Vishal J.

2007-11-01

394

Hot-filament-activated chemical-vapor deposition of carbon: Film growth and filament reactions  

SciTech Connect

Pure glassy carbon films [no x-ray photoelectron spectroscopy (XPS) detectable impurities above the 0.5% level] as thick as 25 000 A have been grown on nearby silicon substrates ([ital T][gt]100 [degree]C) as a result of reactions between a hot tungsten filament and cyclopentane. Above [similar to]2500 [degree]C, cyclopentane-tungsten reactions yield a liquid W/C eutectic which limits filament operation. Below [similar to]2500 [degree]C, resistance changes of the filament and XPS spectra show such reactions form carbides and graphite. It is shown that the temperature dependence of the carbon deposition rate is similar to the sublimation rate of carbon from graphite and tungsten carbide. Moreover, it is also shown that C[sub 1], C[sub 2], and C[sub 3] (carbon monomers, dimers, and trimers) are evaporated from carbarized tungsten and also from graphite. These results suggest that carbon film growth is a consequence of evaporation of carbon from the carbarized tungsten filament, with steady-state film deposition occurring as a result of a quasisteady state in the formation and decomposition of the carbarized tungsten. Carbarization of the tungsten filament is expected for a wide variety of hydrocarbon gases, but evaporation of C species from this carbarized filament should be independent of the way it is produced. These same processes should occur at the tungsten filament during diamond film deposition using the hot-filament chemical-vapor deposition method.

Rye, R.R. (Sandia National Laboratories, Albuquerque, New Mexico 87185 (United States))

1994-07-15

395

Kinetically constrained ring-polymer molecular dynamics for non-adiabatic chemical reactions  

SciTech Connect

We extend ring-polymer molecular dynamics (RPMD) to allow for the direct simulation of general, electronically non-adiabatic chemical processes. The kinetically constrained (KC) RPMD method uses the imaginary-time path-integral representation in the set of nuclear coordinates and electronic states to provide continuous equations of motion that describe the quantized, electronically non-adiabatic dynamics of the system. KC-RPMD preserves the favorable properties of the usual RPMD formulation in the position representation, including rigorous detailed balance, time-reversal symmetry, and invariance of reaction rate calculations to the choice of dividing surface. However, the new method overcomes significant shortcomings of position-representation RPMD by enabling the description of non-adiabatic transitions between states associated with general, many-electron wavefunctions and by accurately describing deep-tunneling processes across asymmetric barriers. We demonstrate that KC-RPMD yields excellent numerical results for a range of model systems, including a simple avoided-crossing reaction and condensed-phase electron-transfer reactions across multiple regimes for the electronic coupling and thermodynamic driving force.

Menzeleev, Artur R.; Bell, Franziska; Miller, Thomas F., E-mail: tfm@caltech.edu [Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125 (United States)

2014-02-14

396

Performance and cost of energy transport and storage systems for dish applications using reversible chemical reactions  

NASA Technical Reports Server (NTRS)

The use of reversible chemical reactions for energy transport and storage for parabolic dish networks is considered. Performance and cost characteristics are estimated for systems using three reactions (sulfur-trioxide decomposition, steam reforming of methane, and carbon-dioxide reforming of methane). Systems are considered with and without storage, and in several energy-delivery configurations that give different profiles of energy delivered versus temperature. Cost estimates are derived assuming the use of metal components and of advanced ceramics. (The latter reduces the costs by three- to five-fold). The process that led to the selection of the three reactions is described, and the effects of varying temperatures, pressures, and heat exchanger sizes are addressed. A state-of-the-art survey was performed as part of this study. As a result of this survey, it appears that formidable technical risks exist for any attempt to implement the systems analyzed in this study, especially in the area of reactor design and performance. The behavior of all components and complete systems under thermal energy transients is very poorly understood. This study indicates that thermochemical storage systems that store reactants as liquids have efficiencies below 60%, which is in agreement with the findings of earlier investigators.

Schredder, J. M.; Fujita, T.

1984-01-01

397

Chemical morphogenesis: recent experimental advances in reaction-diffusion system design and control.  

PubMed

In his seminal 1952 paper, Alan Turing predicted that diffusion could spontaneously drive an initially uniform solution of reacting chemicals to develop stable spatially periodic concentration patterns. It took nearly 40 years before the first two unquestionable experimental demonstrations of such reaction-diffusion patterns could be made in isothermal single phase reaction systems. The number of these examples stagnated for nearly 20 years. We recently proposed a design method that made their number increase to six in less than 3 years. In this report, we formally justify our original semi-empirical method and support the approach with numerical simulations based on a simple but realistic kinetic model. To retain a number of basic properties of real spatial reactors but keep calculations to a minimal complexity, we introduce a new way to collapse the confined spatial direction of these reactors. Contrary to similar reduced descriptions, we take into account the effect of the geometric size in the confinement direction and the influence of the differences in the diffusion coefficient on exchange rates of species with their feed environment. We experimentally support the method by the observation of stationary patterns in red-ox reactions not based on oxihalogen chemistry. Emphasis is also brought on how one of these new systems can process different initial conditions and memorize them in the form of localized patterns of different geometries. PMID:23919126

Szalai, István; Cuiñas, Daniel; Takács, Nándor; Horváth, Judit; De Kepper, Patrick

2012-08-01

398

Chemical morphogenesis: recent experimental advances in reaction–diffusion system design and control  

PubMed Central

In his seminal 1952 paper, Alan Turing predicted that diffusion could spontaneously drive an initially uniform solution of reacting chemicals to develop stable spatially periodic concentration patterns. It took nearly 40 years before the first two unquestionable experimental demonstrations of such reaction–diffusion patterns could be made in isothermal single phase reaction systems. The number of these examples stagnated for nearly 20 years. We recently proposed a design method that made their number increase to six in less than 3 years. In this report, we formally justify our original semi-empirical method and support the approach with numerical simulations based on a simple but realistic kinetic model. To retain a number of basic properties of real spatial reactors but keep calculations to a minimal complexity, we introduce a new way to collapse the confined spatial direction of these reactors. Contrary to similar reduced descriptions, we take into account the effect of the geometric size in the confinement direction and the influence of the differences in the diffusion coefficient on exchange rates of species with their feed environment. We experimentally support the method by the observation of stationary patterns in red-ox reactions not based on oxihalogen chemistry. Emphasis is also brought on how one of these new systems can process different initial conditions and memorize them in the form of localized patterns of different geometries. PMID:23919126

Szalai, István; Cuiñas, Daniel; Takács, Nándor; Horváth, Judit; De Kepper, Patrick

2012-01-01

399

Performance and cost of energy transport and storage systems for dish applications using reversible chemical reactions  

NASA Astrophysics Data System (ADS)

The use of reversible chemical reactions for energy transport and storage for parabolic dish networks is considered. Performance and cost characteristics are estimated for systems using three reactions (sulfur-trioxide decomposition, steam reforming of methane, and carbon-dioxide reforming of methane). Systems are considered with and without storage, and in several energy-delivery configurations that give different profiles of energy delivered versus temperature. Cost estimates are derived assuming the use of metal components and of advanced ceramics. (The latter reduces the costs by three- to five-fold). The process that led to the selection of the three reactions is described, and the effects of varying temperatures, pressures, and heat exchanger sizes are addressed. A state-of-the-art survey was performed as part of this study. As a result of this survey, it appears that formidable technical risks exist for any attempt to implement the systems analyzed in this study, especially in the area of reactor design and performance. The behavior of all components and complete systems under thermal energy transients is very poorly understood. This study indicates that thermochemical storage systems that store reactants as liquids have efficiencies below 60%, which is in agreement with the findings of earlier investigators.

Schredder, J. M.; Fujita, T.

1984-10-01

400

Aerosol chemical and radiative properties in the tropical Atlantic trade winds: The importance of African mineral dust  

NASA Astrophysics Data System (ADS)

This dissertation presents results relevant to aerosol radiative forcing. The focus of this dissertation is the role of mineral dust in atmospheric radiative processes over the tropical Atlantic Ocean. The aerosol mass and light scattering data concurrently measured over the tropical North Atlantic ocean yield a dust mass scattering efficiency of 0.77 m2/g, about a quarter of that measured for non-sea-salt sulfate (nss SO4=) in the North Atlantic marine boundary layer. Because of the high concentration of mineral dust relative to nss SO4= over the tropical North Atlantic, the total scattering by mineral dust is about four times that by nss SO4 = aerosol in this region. On an annual basis, aerosol optical depth is apportioned to: mineral dust 71%, nss- SO4 = 16% and sea salt 13%. The coarse-particle fraction (CPF) (aerodynamic diameter > 1 ?m) of nss SO4= varied from about 21% to 73%, with the highest CPF values associated with African dust events. The CPF nss SO 4= was believed to be a result of the heterogeneous reactions of SO2 (presumably from European sources) with dust particles suspended in the air over North Africa. This study provides the first direct evidence that confirms the importance of dust in sulfate production and resulting the coarse particle sulfate in the tropical Atlantic Ocean region. An important implication is that dust particles may reduce the effectiveness of sulfate aerosol as a radiative forcing agent in many regions where dust events are frequent and where dust concentrations are high. The aerosol scattering coefficient (ASC) measured during this experiment increased by a factor of 1.13 to 1.69 when RH was increased from about 40% to 80%. Through chemical apportioning of ASC, the HGF for sea-salt was found to be 1.8 +/- 0.2, while that of mineral dust was close to unity. This study shows that climate studies must consider the effect of mineral dust not only because of its direct effects on the radiation balance but also because of its effects on the radiative properties of other species that are present in the same air mass.

Li-Jones, Xu

401

Propensity approach to nonequilibrium thermodynamics of a chemical reaction network: Controlling single E-coli ?-galactosidase enzyme catalysis through the elementary reaction steps  

SciTech Connect

In this work, we develop an approach to nonequilibrium thermodynamics of an open chemical reaction network in terms of the elementary reaction propensities. The method is akin to the microscopic formulation of the dissipation function in terms of the Kullback-Leibler distance of phase space trajectories in Hamiltonian system. The formalism is applied to a single oligomeric enzyme kinetics at chemiostatic condition that leads the reaction system to a nonequilibrium steady state, characterized by a positive total entropy production rate. Analytical expressions are derived, relating the individual reaction contributions towards the total entropy production rate with experimentally measurable reaction velocity. Taking a real case of Escherichia coli ?-galactosidase enzyme obeying Michaelis-Menten kinetics, we thoroughly analyze the temporal as well as the steady state behavior of various thermodynamic quantities for each elementary reaction. This gives a useful insight in the relative magnitudes of various energy terms and the dissipated heat to sustain a steady state of the reaction system operating far-from-equilibrium. It is also observed that, the reaction is entropy-driven at low substrate concentration and becomes energy-driven as the substrate concentration rises.

Das, Biswajit; Gangopadhyay, Gautam, E-mail: gautam@bose.res.in [S. N. Bose National Centre For Basic Sciences, Block-JD, Sector-III, Salt Lake, Kolkata 700 098 (India)] [S. N. Bose National Centre For Basic Sciences, Block-JD, Sector-III, Salt Lake, Kolkata 700 098 (India); Banerjee, Kinshuk [Department of Chemistry, University of Calcutta, 92 A.P.C. Road, Kolkata 700 009 (India)] [Department of Chemistry, University of Calcutta, 92 A.P.C. Road, Kolkata 700 009 (India)

2013-12-28

402

Propensity approach to nonequilibrium thermodynamics of a chemical reaction network: Controlling single E-coli ?-galactosidase enzyme catalysis through the elementary reaction stepsa)  

NASA Astrophysics Data System (ADS)

In this work, we develop an approach to nonequilibrium thermodynamics of an open chemical reaction network in terms of the elementary reaction propensities. The method is akin to the microscopic formulation of the dissipation function in terms of the Kullback-Leibler distance of phase space trajectories in Hamiltonian system. The formalism is applied to a single oligomeric enzyme kinetics at chemiostatic condition that leads the reaction system to a nonequilibrium steady state, characterized by a positive total entropy production rate. Analytical expressions are derived, relating the individual reaction contributions towards the total entropy production rate with experimentally measurable reaction velocity. Taking a real case of Escherichia coli ?-galactosidase enzyme obeying Michaelis-Menten kinetics, we thoroughly analyze the temporal as well as the steady state behavior of various thermodynamic quantities for each elementary reaction. This gives a useful insight in the relative magnitudes of various energy terms and the dissipated heat to sustain a steady state of the reaction system operating far-from-equilibrium. It is also observed that, the reaction is entropy-driven at low substrate concentration and becomes energy-driven as the substrate concentration rises.

Das, Biswajit; Banerjee, Kinshuk; Gangopadhyay, Gautam

2013-12-01

403

Importance of molding compound chemical shrinkage in the stress and warpage analysis of PQFPs  

Microsoft Academic Search

This paper addresses the use of finite element (FE) techniques to predict residual warpage in plastic quad flat packs (PQFPs) after encapsulation. Experimental measurements of package warpage are used to validate FE models of the packages. Failure to incorporate mold compound chemical shrinkage into the FE analysis leads to erroneous predictions of package warpage. The warpage sensitivity of different packages

G. Kelly; C. Lyden; W. Lawton; J. Barrett; A. Saboui; H. Pape; H. J. B. Peters

1996-01-01

404

Life cycle assessment of offset printed matter with EDIP97: how important are emissions of chemicals?  

Microsoft Academic Search

Existing product life cycle assessment (LCA) studies on offset printed matter all point at paper as the overall dominating cause of environmental impacts. All studies focus on energy consumption and the dominating role of paper is primarily based on the energy-related impact categories: global warming, acidification and nutrient enrichment. Ecotoxicity and human toxicity, which are related to emissions of chemicals,

Henrik Fred Larsen; Morten Søes Hansen; Michael Hauschild

2009-01-01

405

Quantum chemical and theoretical kinetics study of the O(3P) + C2H2 reaction: a multistate process.  

PubMed

The potential energy surfaces of the two lowest-lying triplet electronic surfaces 3A'' and 3A' for the O(3P) + C2H2 reaction were theoretically reinvestigated, using various quantum chemical methods including CCSD(T), QCISD, CBS-QCI/APNO, CBS-QB3, G2M(CC,MP2), DFT-B3LYP and CASSCF. An efficient reaction pathway on the electronically excited 3A' surface resulting in H(2S) + HCCO(A2A') was newly identified and is predicted to play an important role at higher temperatures. The primary product distribution for the multistate multiwell reaction was then determined by RRKM statistical rate theory and weak-collision master equation analysis using the exact stochastic simulation method. Allowing for nonstatistical behavior of the internal rotation mode of the initial 3A'' adducts, our computed primary-product distributions agree well with the available experimental results, i.e., ca. 80% H(2S) + HCCO(X2A'' + A2A') and 20% CH2(X3B1) + CO(X1sigma+) independent of temperature and pressure over the wide 300-2000 K and 0-10 atm ranges. The thermal rate coefficient k(O + C2H2) at 200-2000 K was computed using multistate transition state theory: k(T) = 6.14 x 10(-15)T (1.28) exp(-1244 K/T) cm3 molecule(-1) s(-1); this expression, obtained after reducing the CBS-QCI/APNO ab initio entrance barriers by 0.5 kcal/mol, quasi-perfectly matches the experimental k(T) data over the entire 200-2000 K range, spanning 3 orders of magnitude. PMID:16722685

Nguyen, Thanh Lam; Vereecken, Luc; Peeters, Jozef

2006-06-01

406

Investigating Arctic Tropospheric Ozone Depletion Through a Flowing Chemical Reaction Method of Halogen Free Radical Measurement  

NASA Astrophysics Data System (ADS)

Arctic tropospheric halogen chemistry has been investigated through the measurement of halogen free radicals, ozone, and gaseous elemental mercury in the lower Arctic troposphere during spring 2008 in a unique sea ice surface environment onboard the research icebreaker CCGS Amundsen. Low-level ozone depletion events were observed beginning in early March, with more extensive events occurring later in the month. Bromine monoxide measurements were conducted using a new, flowing chemical reaction method in addition to established DOAS techniques, and was observed with good agreement at concentrations approaching 40 ppt during periods of significant ozone and mercury depletion. Air mass history was observed for the periods leading to depletion, suggesting a dependence on sea ice contact and ambient temperatures below -22 °C as necessary elements for the onset of halogen-induced tropospheric ozone depletion. Here we discuss our data further with the aim of better understanding how ozone depletion events are triggered.

Tackett, P. J.; Shepson, P. B.; Bottenheim, J. W.; Steffen, A.

2008-12-01

407

Shock-induced hotspot formation and chemical reaction initiation in PETN containing a spherical void  

NASA Astrophysics Data System (ADS)

We present results of reactive molecular dynamics simulations of hotspot formation and chemical reaction initiation in shock-induced compression of pentaerythritol tetranitrate (PETN) with the ReaxFF reactive force field. A supported shockwave is driven through a PETN crystal containing a 20 nm spherical void at a sub-threshold impact velocity of 2 km/s. Formation of a hotspot due to shock-induced void collapse is observed. During void collapse, NO2 is the dominant species ejected from the upstream void surface. Once the ejecta collide with the downstream void surface and the hotspot develops, formation of final products such as N2 and H2O is observed. The simulation provides a detailed picture of how void collapse and hotspot formation leads to initiation at sub-threshold impact velocities.

Shan, Tzu-Ray; Thompson, Aidan P.

2014-05-01

408

Nanocomposite based flexible ultrasensitive resistive gas sensor for chemical reactions studies  

PubMed Central

Room temperature operation, low detection limit and fast response time are highly desirable for a wide range of gas sensing applications. However, the available gas sensors suffer mainly from high temperature operation or external stimulation for response/recovery. Here, we report an ultrasensitive-flexible-silver-nanoparticle based nanocomposite resistive sensor for ammonia detection and established the sensing mechanism. We show that the nanocomposite can detect ammonia as low as 500 parts-per-trillion at room temperature in a minute time. Furthermore, the evolution of ammonia from different chemical reactions has been demonstrated using the nanocomposite sensor as an example. Our results demonstrate the proof-of-concept for the new detector to be used in several applications including homeland security, environmental pollution and leak detection in research laboratories and many others. PMID:23803772

Pandey, Sadanand; Goswami, Gopal K.; Nanda, Karuna K.

2013-01-01

409

Cell-free metabolic engineering: production of chemicals by minimized reaction cascades.  

PubMed

The limited supply of fossil resources demands the development of renewable alternatives to petroleum-based products. Here, biobased higher alcohols such as isobutanol are versatile platform molecules for the synthesis of chemical commodities and fuels. Currently, their fermentation-based production is limited by the low tolerance of microbial production systems to the end products and also by the low substrate flux into cell metabolism. We developed an innovative cell-free approach, utilizing an artificial minimized glycolytic reaction cascade that only requires one single coenzyme. Using this toolbox the cell-free production of ethanol and isobutanol from glucose was achieved. We also confirmed that these streamlined cascades functioned under conditions at which microbial production would have ceased. Our system can be extended to an array of industrially-relevant molecules. Application of solvent-tolerant biocatalysts potentially allows for high product yields, which significantly simplifies downstream product recovery. PMID:23086730

Guterl, Jan-Karl; Garbe, Daniel; Carsten, Jörg; Steffler, Fabian; Sommer, Bettina; Reiße, Steven; Philipp, Anja; Haack, Martina; Rühmann, Broder; Koltermann, Andre; Kettling, Ulrich; Brück, Thomas; Sieber, Volker

2012-11-01

410

Stagnation Point Flow and Mass Transfer with Chemical Reaction past a Stretching/Shrinking Cylinder  

PubMed Central

This paper is about the stagnation point flow and mass transfer with chemical reaction past a stretching/shrinking cylinder. The governing partial differential equations in cylindrical form are transformed into ordinary differential equations by a similarity transformation. The transformed equations are solved numerically using a shooting method. Results for the skin friction coefficient, Schmidt number, velocity profiles as well as concentration profiles are presented for different values of the governing parameters. Effects of the curvature parameter, stretching/shrinking parameter and Schmidt number on the flow and mass transfer characteristics are examined. The study indicates that dual solutions exist for the shrinking cylinder but for the stretching cylinder, the solution is unique. It is observed that the surface shear stress and the mass transfer rate at the surface increase as the curvature parameter increases. PMID:24569547

Najib, Najwa; Bachok, Norfifah; Arifin, Norihan Md.; Ishak, Anuar

2014-01-01

411

Will water act as a photocatalyst for cluster phase chemical reactions? Vibrational overtone-induced dehydration reaction of methanediol  

SciTech Connect

The possibility of water catalysis in the vibrational overtone-induced dehydration reaction of methanediol is investigated using ab initio dynamical simulations of small methanediol-water clusters. Quantum chemistry calculations employing clusters with one or two water molecules reveal that the barrier to dehydration is lowered by over 20 kcal/mol because of hydrogen-bonding at the transition state. Nevertheless, the simulations of the reaction dynamics following OH-stretch excitation show little catalytic effect of water and, in some cases, even show an anticatalytic effect. The quantum yield for the dehydration reaction exhibits a delayed threshold effect where reaction does not occur until the photon energy is far above the barrier energy. Unlike thermally induced reactions, it is argued that competition between reaction and the irreversible dissipation of photon energy may be expected to raise the dynamical threshold for the reaction above the transition state energy. It is concluded that quantum chemistry calculations showing barrier lowering are not sufficient to infer water catalysis in photochemical reactions, which instead require dynamical modeling.

Kramer, Zeb C.; Takahashi, Kaito; Skodje, Rex T. [Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309-0215 (United States); Vaida, Veronica [Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309-0215 (United States); CIRES, University of Colorado, Boulder, Colorado 80309 (United States)

2012-04-28

412

Characterization of chemically modified enzymes for bioremediation-reactions. 1997 annual progress report  

SciTech Connect

'Many, if not most, biological transformation reactions of interest to US Department of Energy (DOE) site remediation involve substrates that are only sparingly soluble in aqueous environments. Hence, destruction of these recalcitrant and toxic materials would benefit tremendously if their degradation could be performed in nonaqueous environments. Organic biocatalysis may be motivated by the nature of the substrate itself, augmented mass transport, ease of product recovery, or novel reaction pathways afforded by the organic solvent. For instance, polychlorinated biphenyls (PCBs) are sparingly soluble in water, but may be more effectively processed when solubilized by organic liquids. However, naturally-occurring enzymes are not soluble in organic solvents. Indeed, most spontaneously denature and, depending on the solvent used, typically form inactive and insoluble precipitates. The objective of the current work is to gain a fundamental understanding of the molecular and catalytic properties of enzymes that have been chemically-modified so that they are catalytically-active and chemically-thermally-stable in organic solvents. The premise for this study is that highly stable enzymes which are catalytically active in both water and in a range of organic solvents are optimally suited for bioremediation where substrates of interest are more soluble and may be processed with greater specificity in nonaqueous solvents. The proposed research program will enable the development of nonaqueous bioremediation technologies for the treatment of DOE sites contaminated with aqueous-insoluble organic compounds. Such compounds may include dense nonaqueous phase liquids, trichloroethylene (TCE), trichloroacetic acid, trans-dichloroethylene, diesel fuel, and PCBs. These compounds have been identified as targets for technology development in the ``EM Technology Needs Database,'''' and are contaminants at the following DOE sites: K-25 Site plumes; ORNL WAGS 1, 4, and 5; Paducah plumes; Portsmouth plumes; the X-701B Holding Pond; and the Y-12 Poplar Creek and Bear Creek Watersheds.'

Kaufman, E.N. [Oak Ridge National Lab., TN (US); Adams, M.W.W. [Univ. of Georgia, Athens, GA (US)

1997-09-01

413

Convective stability in the presence of a catalytic chemical reaction. I.  

NASA Technical Reports Server (NTRS)

A linear analysis of hydrodynamic stability has been applied to a problem in which a fluid mixture is contained between two horizontal planes. One species diffuses to the lower plane where it is destroyed by a rapid exothermic or endothermic catalytic reaction. Results show that important coupling takes place between thermal and concentration fields. This coupling gives rise to unusual stabilizing or destabilizing effects, depending upon the value of Lewis number. Several examples are discussed. It is also shown how the results can be applied to other problems involving heat and mass transfer.

Wankat, P. C.; Schowalter, W. R.

1971-01-01

414

Regional chemical setting of the Apollo 16 landing site and the importance of the Kant Plateau  

NASA Technical Reports Server (NTRS)

Orbital X-ray data from the Apollo 16 region indicate that physiographic units identified before the lunar mission can be classified as chemical units as well. The Descartes Mountains, however, appear to be an extension of the Kant Plateau composition that is unusually anorthositic and resembles farside terra. The Cayley Plains have closer affinities to basaltic materials than terra materials, physically, spectrally and chemically. The Theophilus impact, 330 km east of the landing site, excavated magnesium-rich basalts from below less-magnesian flows in Mare Nectaris; but, mafic ejecta was substantially blocked from the Apollo 16 site by the Kant Plateau that rises 5 km above the level of the mare. Apollo 16 soil samples from stations selected to collect either Descartes Mountains material or Cayley Plains material were surprisingly similar. However, they do, indeed, show the chemical trends indicative of the two units as defined by the orbiting geochemistry detectors. The Kant Plateau and Descartes Mountains material may be among the rare nearside examples of a plagioclase-rich cumulate of the primordial magma ocean.

Andre, C. G.; El-Baz, F.

1982-01-01

415

Reactive force fields for surface chemical reactions: A case study with hydrogen dissociation on Pd surfaces.  

PubMed

An approach based on reactive force fields is applied to the parametrization of potential energy surface (PES) for chemical reactions on surfaces with a benchmark system, H(2)/Pd(111). We show that a simple reactive force field based on the second moment approximation does not allow for obtaining reliable results of reaction dynamics for the considered system. With a more elaborate reactive force field, i.e., reactive bond order (REBO) force field, we succeeded in obtaining a reliable PES for H(2)/Pd(111). The accuracy of the constructed REBO force field is carefully checked through various tests including the comparison not only between energies calculated with density functional theory and those with REBO force field but also between the available results of ab initio molecular dynamics simulations and those with our force field. Moreover, our REBO force field is endowed with some transferability since the force field constructed with a database containing only information on H(2)/Pd(111) allows for obtaining also accurate results for H(2)/Pd(100) and qualitatively correct results for H(2)/Pd(110) without any refitting. With the help of our reactive force field, the molecular dynamics simulation for the dissociation of H(2) on the considered Pd surfaces is speeded up by five orders of magnitude compared to ab initio molecular dynamics method. The demonstrated reliability and the very high computational efficiency of reactive force fields open extremely attractive perspectives for studying large-scale complex reacting systems. PMID:20078177

Xiao, Y; Dong, W; Busnengo, H F

2010-01-01

416

EVALUATION OF CHEMICAL REACTION MECHANISMS FOR PHOTOCHEMICAL SMOG. PART 3. SENSITIVITY OF EKMA (EMPIRICAL KINETIC MODELING APPROACH) TO CHEMICAL MECHANISM AND INPUT PARAMETERS  

EPA Science Inventory

Six chemical reaction mechanisms for photochemical smog were used to study the effect of input parameters on volatile organic compound (VOC) control requirements needed to reduce ozone. The parameters studied were initial VOC composition, dilution rate, post 8-A.M. emissions, bas...

417

Direct spatiotemporal analysis of femtosecond laser-induced plasma-mediated chemical reactions  

NASA Astrophysics Data System (ADS)

Localized, micron to millimetre-scale plasmas resulting from the fleeting interaction between ultrashort laser pulses and matter have been studied extensively in inert atmospheres. In spite of recent interest in reactive plasmas as a nanofabrication tool, ultrashort pulsed laser ablation in reactive gas atmospheres has undergone little study. In this study, we develop a methodology combining time-resolved optical emission spectroscopy and spectrally filtered time-gated fast photography to directly observe and analyse plasma-mediated chemical reactions that occur when laser ablation is performed in reactive gases. Specifically, we compare the ablation of silicon dioxide in an atmosphere of xenon difluoride gas to its ablation in nitrogen and xenon atmospheres. We show that when xenon difluoride molecules are collisionally driven into an excited state by the silicon plasma produced during laser-induced decomposition of the solid substrate, the gas undergoes dissociation. The resulting fluorine radicals react spontaneously with the silicon plasma to produce volatile fluorinated silicon compounds. In particular, mass spectroscopy shows that the primary reaction byproduct is SiF2 with small amounts of SiF and SiF4. The high spatial and temporal resolution of our methodology reveals a slowly expanding plume having an atomic silicon core with a XeF? shell that persists for less than 300 ns. As the silicon is fluorinated, the optical emission due to excited silicon is quenched. The absence of a silicon signal after 300 ns establishes this as the upper limit of the reaction lifetime given the conditions of the experiment.

Straw, Marcus; Randolph, Steven

2014-03-01

418

Noise-Induced Modulation of the Relaxation Kinetics around a Non-Equilibrium Steady State of Non-Linear Chemical Reaction Networks  

PubMed Central

Stochastic effects from correlated noise non-trivially modulate the kinetics of non-linear chemical reaction networks. This is especially important in systems where reactions are confined to small volumes and reactants are delivered in bursts. We characterise how the two noise sources confinement and burst modulate the relaxation kinetics of a non-linear reaction network around a non-equilibrium steady state. We find that the lifetimes of species change with burst input and confinement. Confinement increases the lifetimes of all species that are involved in any non-linear reaction as a reactant. Burst monotonically increases or decreases lifetimes. Competition between burst-induced and confinement-induced modulation may hence lead to a non-monotonic modulation. We quantify lifetime as the integral of the time autocorrelation function (ACF) of concentration fluctuations around a non-equilibrium steady state of the reaction network. Furthermore, we look at the first and second derivatives of the ACF, each of which is affected in opposite ways by burst and confinement. This allows discriminating between these two noise sources. We analytically derive the ACF from the linear Fokker–Planck approximation of the chemical master equation in order to establish a baseline for the burst-induced modulation at low confinement. Effects of higher confinement are then studied using a partial-propensity stochastic simulation algorithm. The results presented here may help understand the mechanisms that deviate stochastic kinetics from its deterministic counterpart. In addition, they may be instrumental when using fluorescence-lifetime imaging microscopy (FLIM) or fluorescence-correlation spectroscopy (FCS) to measure confinement and burst in systems with known reaction rates, or, alternatively, to correct for the effects of confinement and burst when experimentally measuring reaction rates. PMID:21297975

Ramaswamy, Rajesh; Sbalzarini, Ivo F.; González-Segredo, Nélido

2011-01-01

419

Control of Convective Dissolution by Chemical Reactions: General Classification and Application to CO2 Dissolution in Reactive Aqueous Solutions  

NASA Astrophysics Data System (ADS)

In partially miscible two-layer systems within a gravity field, buoyancy-driven convective motions can appear when one phase dissolves with a finite solubility into the other one. We investigate the influence of chemical reactions on such convective dissolution by a linear stability analysis of a reaction-diffusion-convection model. We show theoretically that a chemical reaction can either enhance or decrease the onset time of the convection, depending on the type of density profile building up in time in the reactive solution. We classify the stabilizing and destabilizing scenarios in a parameter space spanned by the solutal Rayleigh numbers. As an example, we experimentally demonstrate the possibility to enhance the convective dissolution of gaseous CO2 in aqueous solutions by a classical acid-base reaction.

Loodts, V.; Thomas, C.; Rongy, L.; De Wit, A.

2014-09-01

420

Control of convective dissolution by chemical reactions: general classification and application to CO(2) dissolution in reactive aqueous solutions.  

PubMed

In partially miscible two-layer systems within a gravity field, buoyancy-driven convective motions can appear when one phase dissolves with a finite solubility into the other one. We investigate the influence of chemical reactions on such convective dissolution by a linear stability analysis of a reaction-diffusion-convection model. We show theoretically that a chemical reaction can either enhance or decrease the onset time of the convection, depending on the type of density profile building up in time in the reactive solution. We classify the stabilizing and destabilizing scenarios in a parameter space spanned by the solutal Rayleigh numbers. As an example, we experimentally demonstrate the possibility to enhance the convective dissolution of gaseous CO_{2} in aqueous solutions by a classical acid-base reaction. PMID:25259984

Loodts, V; Thomas, C; Rongy, L; De Wit, A

2014-09-12

421

Surface chemical reactions during electron beam irradiation of nanocrystalline CaS:Ce3+ phosphor  

NASA Astrophysics Data System (ADS)

The effects of accelerating voltage (0.5-5 keV) on the green cathodoluminescence (CL) of CaS:Ce3+ nanocrystalline powder phosphors is reported. An increase in the CL intensity was observed from the powders when the accelerating voltage was varied from 0.5 to 5 keV, which is a relevant property for a phosphor to be used in field emission displays (FEDs). The CL degradation induced by prolonged electron beam irradiation was analyzed using CL spectroscopy, x-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES). The AES data showed the decrease in the S peak intensity and an increase in the O peak intensity during electron bombardment. The CL intensity was found to decrease to 30% of its original intensity after about 50 C/cm2. XPS was used to study the chemical composition of the CaS:Ce3+ nanophosphor before and after degradation. The XPS data confirms that a nonluminescent CaSO4 layer has formed on the surface during the degradation process, which may partially be responsible for the CL degradation. The electron stimulated surface chemical reaction mechanism was used to explain the effects of S desorption and the formation of the nonluminescent CaSO4 layer on the surface.

Kumar, Vinay; Mishra, Varun; Pitale, Shreyas S.; Nagpure, I. M.; Coetsee, E.; Ntwaeaborwa, O. M.; Terblans, J. J.; Swart, H. C.

2010-06-01

422

Chemical nonequilibrium and deconfinement in 200A GeV sulphur induced reactions  

NASA Astrophysics Data System (ADS)

We interpret hadronic particle abundances produced in S-Au/W/Pb 200A GeV reactions in terms of the final state hadronic phase space model and determine by a data fit of the chemical hadron freeze-out parameters. Allowing for the flavor abundance nonequilibrium a highly significant fit to experimental particle abundance data emerges, which supports the possibility of strangeness distillation. We find under different strategies stable values for freeze-out temperature Tf=143+/-3 MeV, baryochemical potential ?B=173+/-6 MeV, ratio of strangeness (?s) and light quark (?q) phase space occupancies ?s/?q=0.60+/-0.02, and ?q=1.22+/-0.05 without accounting for collective expansion (radial flow). When introducing flow effects which allow a consistent description of the transverse mass particle spectra, yielding \\|v-->c\\|=0.49+/-0.01 c, we find ?s/?q=0.69+/-0.03, ?q=1.41+/-0.08. The strange quark fugacity is fitted at ?s=1.00+/-0.02 suggesting chemical freeze-out directly from the deconfined phase.

Letessier, Jean; Rafelski, Johann

1999-02-01

423

Chemical reactions involved in the initiation of hot corrosion of IN-738  

NASA Technical Reports Server (NTRS)

Sodium-sulfate-induced hot corrosion of preoxidized IN-738 was studied at 975 C with special emphasis placed on the processes occurring during the long induction period. Thermogravimetric tests were run for predetermined periods of time, and then one set of specimens was washed with water. Chemical analysis of the wash solutions yielded information about water soluble metal salts and residual sulfate. A second set of samples was cross sectioned dry and polished in a nonaqueous medium. Element distributions within the oxide scale were obtained from electron microprobe X-ray micrographs. Evolution of SO was monitored throughout the thermogravimetric tests. Kinetic rate studies were performed for several pertinent processes; appropriate rate constants were obtained from the following chemical reactions; Cr203 + 2 Na2S04(1) + 3/2 02 yields 2 Na2Cr04(1) + 2 S03(g)n TiO2 + Na2S04(1) yields Na20(T102)n + 503(g)n T102 + Na2Cro4(1) yields Na2(T102)n + Cr03(g).

Fryburg, G. C.; Kohl, F. J.; Stearns, C. A.

1984-01-01

424

Chemical mechanisms and reaction rates for the initiation of hot corrosion of IN-738  

NASA Technical Reports Server (NTRS)

Sodium-sulfate-induced hot corrosion of preoxidized IN-738 was studied at 975 C with special emphasis placed on the processes occurring during the long induction period. Thermogravimetric tests were run for predetermined periods of time, and then one set of specimens was washed with water. Chemical analysis of the wash solutions yielded information about water soluble metal salts and residual sulfate. A second set of samples was cross sectioned dry and polished in a nonaqueous medium. Element distributions within the oxide scale were obtained from electron microprobe X-ray micrographs. Evolution of SO was monitored throughout the thermogravimetric tests. Kinetic rate studies were performed for several pertinent processes; appropriate rate constants were obtained from the following chemical reactions: Cr2O3 + 2 Na2SO4(1) + 3/2 O2 yields 2 Na2CrO4(1) + 2 SO3(g)n TiO2 + Na2SO4(1) yields Na2O(TiO2)n + SO3(g)n TiO2 + Na2CrO4(1) yields Na2O(TiO2)n + CrO3(g).

Fryburg, G. C.; Kohl, F. J.; Stearns, C. A.

1984-01-01

425

Strength advantages of chemically polished boron fibers before and after reaction with aluminum  

NASA Technical Reports Server (NTRS)

In order to determine their strength potential, the fracture properties of different types of commercial boron fibers were measured before and after application of secondary strengthening treatments. The principal treatments employed were a slight chemical polish, which removed low strength surface flaws, and a heat treatment in oxygen, which contracted the fibers and thereby compressed intrinsic bulk flaws. Those fiber types most significantly strengthened were 200 to 400 micrometers (8 to 16 mil) diameter boron on tungsten fibers produced in a single chemical vapor deposition reactor. The slight polish increased average tensile strenghts from 3.4 to 4.4 CN/m2 (500 to 640 ksi) and reduced coefficients of variation from about 15 to 3 percent. The oxygen heat treatment plus slight polish further improved average strengths to 5.5 GN/m2 (800 ksi) with coefficients near 3 percent. To ascertain whether these excellent properties could be retained after fabrication of B/Al composites, as produced and polished 203 micrometers (8 mil) fibers were thinly coated with aluminum, heat treated at B/Al fabrication temperatures, and then tested in tension and flexure at room temperature. The pre-polished fibers were observed to retain their superior strengths to higher temperatures than the as-produced fibers even though both were subjected to the same detrimental reaction with aluminum.

Dicarlo, J. A.; Smith, R. J.

1982-01-01

426

Surface chemical reactions during electron beam irradiation of nanocrystalline CaS:Ce{sup 3+} phosphor  

SciTech Connect

The effects of accelerating voltage (0.5-5 keV) on the green cathodoluminescence (CL) of CaS:Ce{sup 3+} nanocrystalline powder phosphors is reported. An increase in the CL intensity was observed from the powders when the accelerating voltage was varied from 0.5 to 5 keV, which is a relevant property for a phosphor to be used in field emission displays (FEDs). The CL degradation induced by prolonged electron beam irradiation was analyzed using CL spectroscopy, x-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES). The AES data showed the decrease in the S peak intensity and an increase in the O peak intensity during electron bombardment. The CL intensity was found to decrease to 30% of its original intensity after about 50 C/cm{sup 2}. XPS was used to study the chemical composition of the CaS:Ce{sup 3+} nanophosphor before and after degradation. The XPS data confirms that a nonluminescent CaSO{sub 4} layer has formed on the surface during the degradation process, which may partially be responsible for the CL degradation. The electron stimulated surface chemical reaction mechanism was used to explain the effects of S desorption and the formation of the nonluminescent CaSO{sub 4} layer on the surface.

Kumar, Vinay; Pitale, Shreyas S.; Nagpure, I. M.; Coetsee, E.; Ntwaeaborwa, O. M.; Terblans, J. J.; Swart, H. C. [Department of Physics, University of the Free State, P.O. Box 339, Bloemfontein ZA9300 (South Africa); Mishra, Varun [Department of Physics, Lovely Institute of Engineering-POLY, Lovely Professional University, Phagwara 144 402, Punjab (India)

2010-06-15

427

77 FR 76302 - Importer of Controlled Substances; Notice of Application; ISP Freetown Fine Chemicals  

Federal Register 2010, 2011, 2012, 2013

...of controlled substance listed in schedule II. The company plans to import the listed controlled substance to manufacture amphetamine. Any bulk manufacturer who is presently, or is applying to be, registered with DEA to manufacture such basic class...

2012-12-27

428

A method for incorporating equilibrium chemical reactions into multiphase flow models for CO2 storage  

NASA Astrophysics Data System (ADS)

CO2 injection and storage in deep saline aquifers involves many coupled processes, including multiphase flow, heat and mass transport, rock deformation and mineral precipitation and dissolution. Coupling is especially critical in carbonate aquifers, where minerals will tend to dissolve in response to the dissolution of CO2 into the brine. The resulting neutralization will drive further dissolution of both CO2 and calcite. This suggests that large cavities may be formed and that proper simulation may require full coupling of reactive transport and multiphase flow. We show that solving the latter may suffice whenever two requirements are met: (1) all reactions can be assumed to occur in equilibrium and (2) the chemical system can be calculated as a function of the state variables of the multiphase flow model (i.e., liquid and gas pressure, and temperature). We redefine the components of multiphase flow codes (traditionally, water and CO2), so that they are conservative for all reactions of the chemical system. This requires modifying the traditional constitutive relationships of the multiphase flow codes, but yields the concentrations of all species and all reaction rates by simply performing speciation and mass balance calculations at the end of each time step. We applied this method to the H2O-CO2-Na-Cl-CaCO3 system, so as to model CO2 injection into a carbonate aquifer containing brine. Results were very similar to those obtained with traditional formulations, which implies that full coupling of reactive transport and multi-phase flow is not really needed for this kind of systems, but the resulting simplifications may make it advisable even for cases where the above requirements are not met. Regarding the behavior of carbonate rocks, we find that porosity development near the injection well is small because of the low solubility of calcite. Moreover, dissolution concentrates at the front of the advancing CO2 plume because the brine below the plume tends to reach high CO2 concentrations quite rapidly. We conclude that carbonate dissolution needs not to be feared.

Saaltink, Maarten W.; Vilarrasa, Victor; De Gaspari, Francesca; Silva, Orlando; Carrera, Jesús; Rötting, Tobias S.

2013-12-01

429

Sub-grid scale modeling of heterogeneous chemical reactions and transport in full-scale catalytic converters  

Microsoft Academic Search

This article presents a novel approach to treat heterogeneous catalytic reactions occurring in porous or honeycomb monoliths. The approach allows accurate modeling of full-scale catalytic converters with low computational cost. In this approach, the entire catalytic monolith is treated as an anisotropic porous medium, and sub-grid scale models are employed to represent the heterogeneous chemical reactions occurring at the solid-fluid

Sandip Mazumder; Debasis Sengupta

2002-01-01

430

Dynamic Transition in the Structure of an Energetic Crystal during Chemical Reactions at Shock Front Prior to Detonation  

Microsoft Academic Search

Mechanical stimuli in energetic materials initiate chemical reactions at shock fronts prior to detonation. Shock sensitivity measurements provide widely varying results, and quantum-mechanical calculations are unable to handle systems large enough to describe shock structure. Recent developments in reactive force-field molecular dynamics (ReaxFF-MD) combined with advances in parallel computing have paved the way to accurately simulate reaction pathways along with

Ken-Ichi Nomura; Rajiv K. Kalia; Aiichiro Nakano; Priya Vashishta; Adri C. T. van Duin; William A. Goddard III

2007-01-01

431

Optimization of chemical reactions between alumina\\/silica fibres and aluminium-magnesium alloys during composite processing  

Microsoft Academic Search

An Al-Si-;Cu-Mg alloy reinforced with alumina\\/silica fibres (Fiberfrax, alumina\\/silica ratio=45\\/55) has been extensively\\u000a characterized in terms of microstructure, interfacial chemical reactions and mechanical properties. The composite was fabricated\\u000a by squeeze casting. The above characteristics were measured as a function of (a) calcination temperature of the fibre preform\\u000a before infiltration, and (b) subsequent composite heat treatment. The main reaction that occurs

W. S. WOLBACH; S. R. BRYAN; G. L SHOEMAKER; T. W KRUCEK; R. D MAIER; K. K SONI; J. M CHABALA; R MOGILEVSKY; R LEVI-SETTI

1997-01-01

432

Cycle Evaluations of Reversible Chemical Reactions for Solar Thermochemical Energy Storage in Support of Concentrating Solar Power Generation Systems  

SciTech Connect

The production and storage of thermochemical energy is a possible route to increase capacity factors and reduce the Levelized Cost of Electricity from concentrated solar power generation systems. In this paper, we present the results of cycle evaluations for various thermochemical cycles, including a well-documented ammonia closed-cycle along with open- and closed-cycle versions of hydrocarbon chemical reactions. Among the available reversible hydrocarbon chemical reactions, catalytic reforming-methanation cycles are considered; specifically, various methane-steam reforming cycles are compared to the ammonia cycle. In some cases, the production of an intermediate chemical, methanol, is also included with some benefit being realized. The best case, based on overall power generation efficiency and overall plant capacity factor, was found to be an open cycle including methane-steam reforming, using concentrated solar energy to increase the chemical energy content of the reacting stream, followed by combustion to generate heat for the heat engine.

Krishnan, Shankar; Palo, Daniel R.; Wegeng, Robert S.

2010-07-25

433

Influence of Chemical Kinetics on Postcolumn Reaction in a Capillary Taylor Reactor with Catechol Analytes and Photoluminescence Following Electron Transfer  

PubMed Central

Postcolumn derivatization reactions can enhance detector sensitivity and selectivity, but their successful combination with capillary liquid chromatography has been limited because of the small peak volumes in capillary chromatography. A capillary Taylor reactor (CTR), developed in our laboratory, provides simple and effective mixing and reaction in a 25-?m-radius postcolumn capillary. Homogenization of reactant streams occurs by radial diffusion, and a chemical reaction follows. Three characteristic times for a given reaction process can be predicted using simple physical and chemical parameters. Two of these times are the homogenization time, which governs how long it takes the molecules in the analyte and reagent streams to mix, and the reaction time, which governs how long the molecules in a homogeneous solution take to react. The third characteristic time is an adjustment to the reaction time called the start time, which represents an estimate of the average time the analyte stream spends without exposure to reagent. In this study, laser-induced fluorescence monitored the extent of the postcolumn reaction (reduction of Os(bpy)33+ by analyte to the photoluminescent Os(bpy)32+) in a CTR. The reaction time depends on the reaction rates. Analysis of product versus time data yielded second-order reaction rate constants between the PFET reagent, tris(2,2?-bipyridine)osmium, and standards ((ferrocenylmethyl)trimethylammonium cation and p-hydroquinone) or catechols (dopamine, epinephrine, norepinephrine, 3, 4-dihydroxyphenylacetic acid. The extent of the reactions in a CTR were then predicted from initial reaction conditions and compared to experimental results. Both the theory and experimental results suggested the reactions of catechols were generally kinetically controlled, while those of the standards were controlled by mixing time (1–2 s). Thus, the extent of homogenization can be monitored in a CTR using the relatively fast reaction of the reagent and p-hydroquinone. Kinetically controlled reactions of catechols, however, could be also completed in a reasonable time at increased reagent concentration. A satisfactory reactor, operating at 1.7 cm/s (2 ?L/min) velocity with solutes having diffusion coefficients in the 5 × 10?6 cm2/s range, can be constructed from 8.0 cm of 25-?m-radius capillary. Slower reactions require longer reaction times, but theoretical calculations expect that a CTR does not broaden a chromatographic peak (N = 14 000) from a 100-?m-capillary chromatography column by 10% if the pseudo-first-order rate constant is larger than 0.1 s?1. PMID:15858975

Jung, Moon Chul; Weber, Stephen G.

2006-01-01

434

The Volumetric Particle Approach for Concentration Fluctuations and Chemical Reactions in Lagrangian Particle and Particle-grid Models  

NASA Astrophysics Data System (ADS)

A new approach is proposed to predict concentration fluctuations in the framework of one-particle Lagrangian stochastic models. The approach is innovative since it allows the computation of concentration fluctuations in dispersing plumes using a Lagrangian one-particle model with micromixing but with no need for the simulating of background particles. The extension of the model for the treatment of chemically reactive plumes is also accomplished and allows the computation of plume-related chemical reactions in a Lagrangian one-particle framework separately from the background chemical reactions, accounting for the effect of concentration fluctuations on chemical reactions in a general, albeit approximate, manner. These characteristics should make the proposed approach an ideal tool for plume-in-grid calculations in chemistry transport models. The results are compared to the wind-tunnel experiments of Fackrell and Robins (J Fluid Mech, 117:1-26, 1982) for plume dispersion in a neutral boundary layer and to the measurements of Legg et al. (Boundary-Layer Meteorol, 35:277-302, 1986) for line source dispersion in and above a model canopy. Preliminary reacting plume simulations are also shown comparing the model with the experimental results of Brown and Bilger (J Fluid Mech, 312:373-407, 1996; Atmos Environ, 32:611-628, 1998) to demonstrate the feasibility of computing chemical reactions in the proposed framework.

Cassiani, Massimo

2013-02-01

435

LSENS: A General Chemical Kinetics and Sensitivity Analysis Code for homogeneous gas-phase reactions. Part 3: Illustrative test problems  

NASA Technical Reports Server (NTRS)

LSENS, the Lewis General Chemical Kinetics and Sensitivity Analysis Code, has been developed for solving complex, homogeneous, gas-phase chemical kinetics problems and contains sensitivity analysis for a variety of problems, including nonisothermal situations. This report is part 3 of a series of three reference publications that describe LSENS, provide a detailed guide to its usage, and present many example problems. Part 3 explains the kinetics and kinetics-plus-sensitivity analysis problems supplied with LSENS and presents sample results. These problems illustrate the various capabilities of, and reaction models that can be solved by, the code and may provide a convenient starting point for the user to construct the problem data file required to execute LSENS. LSENS is a flexible, convenient, accurate, and efficient solver for chemical reaction problems such as static system; steady, one-dimensional, inviscid flow; reaction behind incident shock wave, including boundary layer correction; and perfectly stirred (highly backmixed) reactor. In addition, the chemical equilibrium state can be computed for the following assigned states: temperature and pressure, enthalpy and pressure, temperature and volume, and internal energy and volume. For static problems the code computes the sensitivity coefficients of the dependent variables and their temporal derivatives with respect to the initial values of the dependent variables and/or the three rate coefficient parameters of the chemical reactions.

Bittker, David A.; Radhakrishnan, Krishnan

1994-01-01

436

Importance of ticks and their chemical and immunological control in livestock*  

PubMed Central

The medical and economic importance of ticks has long been recognized due to their ability to transmit diseases to humans and animals. Ticks cause great economic losses to livestock, and adversely affect livestock hosts in several ways. Loss of blood is a direct effect of ticks acting as potential vector for haemo-protozoa and helminth parasites. Blood sucking by large numbers of ticks causes reduction in live weight and anemia among domestic animals, while their bites also reduce the quality of hides. However, major losses caused by ticks are due to their ability to transmit protozoan, rickettsial and viral diseases of livestock, which are of great economic importance world-wide. There are quite a few methods for controlling ticks, but every method has certain shortcomings. The present review is focused on ticks importance and their control. PMID:17048307

Rajput, Zahid Iqbal; Hu, Song-hua; Chen, Wan-jun; Arijo, Abdullah G.; Xiao, Chen-wen

2006-01-01

437

The initiation of methane/air autoignition: the important chemical components for various initial conditions  

NASA Astrophysics Data System (ADS)

A reactive system will be considered, the slow dynamics of which is characterized by time scales that are of explosive character; i.e., the components of the system that generate them tend to lead the system away from equilibrium. In particular, the initiation of a methane/air mixture autoignition will be considered for various initial temperatures and pressures. The species that relate to the explosive time scales and reactions that are responsible for the generation of these time scales will be identified. The analysis will be based on the Computational Singular Perturbation (CSP) algorithm, which is employed for the construction of the the reduced system that governs the long range (slow) evolution of the system. It will be demonstrated that an excellent agreement with the existing literature is obtained.

Manias, D. M.; Goussis, D. A.

2015-01-01

438

Conjugated processes of the chemical transformation of sulfur dioxide under the effect of chain gas-phase reactions  

NASA Astrophysics Data System (ADS)

The effect sulfur dioxide has on the dynamics of the spontaneous ignition of hydrogen-oxygen mixtures is studied. Additives of SO2 have no negative effect on spontaneous ignition and undergo chemical conversion to form elemental sulfur. The results are analyzed using the theory of branched chain reactions along with data on SO2 conversion under the action of chain reactions of hydrocarbon oxidation and slow hydrogen oxidation. The transformations classified as parallel reactions from the viewpoint of formal kinetics could actually be conjugated radical-chain processes.

Mantashyan, A. A.

2015-01-01

439

Combining biological and chemical controls for the management of red imported fire ants (Hymenoptera: Formicidae)  

Technology Transfer Automated Retrieval System (TEKTRAN)

Two South American natural enemies of imported fire ants were first detected or released in the United States approximately 10 years ago. The fire ant pathogen, Thelohania solenopsae Knell, Allen, and Hazard, was found in the U.S. in 1996 and a parasitic phorid fly from Brazil, Pseudacteon tricuspi...

440

Influence of temperature and packaging on physiological and chemical profiles of imported litchi fruit  

Microsoft Academic Search

The aim of this study was to detail the physiological and biochemical changes in non-adulterated and commercially-treated litchi fruit stored in different packaging films under different storage temperatures. Litchi fruit cv. Mauritius treated with either SO2 and acid (commercially-treated fruit), or free from both SO2 and acid (non-adulterated fruit), were imported from Israel and packed using two different packaging films

Nettra Somboonkaew; Leon A. Terry

2011-01-01

441

The small-voxel tracking algorithm for simulating chemical reactions among diffusing molecules.  

PubMed

Simulating the evolution of a chemically reacting system using the bimolecular propensity function, as is done by the stochastic simulation algorithm and its reaction-diffusion extension, entails making statistically inspired guesses as to where the reactant molecules are at any given time. Those guesses will be physically justified if the system is dilute and well-mixed in the reactant molecules. Otherwise, an accurate simulation will require the extra effort and expense of keeping track of the positions of the reactant molecules as the system evolves. One molecule-tracking algorithm that pays careful attention to the physics of molecular diffusion is the enhanced Green's function reaction dynamics (eGFRD) of Takahashi, T?nase-Nicola, and ten Wolde [Proc. Natl. Acad. Sci. U.S.A. 107, 2473 (2010)]. We introduce here a molecule-tracking algorithm that has the same theoretical underpinnings and strategic aims as eGFRD, but a different implementation procedure. Called the small-voxel tracking algorithm (SVTA), it combines the well known voxel-hopping method for simulating molecular diffusion with a novel procedure for rectifying the unphysical predictions of the diffusion equation on the small spatiotemporal scale of molecular collisions. Indications are that the SVTA might be more computationally efficient than eGFRD for the problematic class of non-dilute systems. A widely applicable, user-friendly software implementation of the SVTA has yet to be developed, but we exhibit some simple examples which show that the algorithm is computationally feasible and gives plausible results. PMID:25527927

Gillespie, Daniel T; Seitaridou, Effrosyni; Gillespie, Carol A

2014-12-21

442

The small-voxel tracking algorithm for simulating chemical reactions among diffusing molecules  

NASA Astrophysics Data System (ADS)

Simulating the evolution of a chemically reacting system using the bimolecular propensity function, as is done by the stochastic simulation algorithm and its reaction-diffusion extension, entails making statistically inspired guesses as to where the reactant molecules are at any given time. Those guesses will be physically justified if the system is dilute and well-mixed in the reactant molecules. Otherwise, an accurate simulation will require the extra effort and expense of keeping track of the positions of the reactant molecules as the system evolves. One molecule-tracking algorithm that pays careful attention to the physics of molecular diffusion is the enhanced Green's function reaction dynamics (eGFRD) of Takahashi, T?nase-Nicola, and ten Wolde [Proc. Natl. Acad. Sci. U.S.A. 107, 2473 (2010)]. We introduce here a molecule-tracking algorithm that has the same theoretical underpinnings and strategic aims as eGFRD, but a different implementation procedure. Called the small-voxel tracking algorithm (SVTA), it combines the well known voxel-hopping method for simulating molecular diffusion with a novel procedure for rectifying the unphysical predictions of the diffusion equation on the small spatiotemporal scale of molecular collisions. Indications are that the SVTA might be more computationally efficient than eGFRD for the problematic class of non-dilute systems. A widely applicable, user-friendly software implementation of the SVTA has yet to be developed, but we exhibit some simple examples which show that the algorithm is computationally feasible and gives plausible results.

Gillespie, Daniel T.; Seitaridou, Effrosyni; Gillespie, Carol A.

2014-12-01